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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Comparison of Acoustic Impedance Eduction Techniques for Locally-Reacting Liners

Typical acoustic liners used in current aircraft inlets and aft-fan ducts consist of some type of perforated facesheet bonded to a honeycomb core. A number of techniques for determining the acoustic impedance of these locallyreacting liners have been developed over the last five decades. In addition, a number of models have been developed to predict the acoustic impedance of locallyreacting liners in the presence of grazing flow, and to use that information together with aeroacoustic propagation codes to assess the noise absorption provided by these liners. These prediction models have incorporated the results from databases acquired with specific impedance eduction techniques. Thus, while these prediction models are acceptable for liners that are similar to those tested in these databases, their application to new liner configurations must be viewed with caution. The primary purpose of this paper is to provide a comparison of impedance eduction techniques that have been implemented at various aerospace research laboratories in the United States (NASA Langley Research Center, General Electric Aircraft Engines, B. F. Goodrich and Boeing). A secondary purpose is to provide data for liner configurations that extend the porosity range beyond that which has been previously used in common aircraft engine nacelles. Two sets of liners were designed to study the effects of three parameters: perforate hole diameter, facesheet thickness and porosity. These two sets of liners were constructed for testing in each of the laboratories listed above. The first set of liners was designed to fit into the NASA Langley and Boeing test facilities. The second set was designed to fit into the General Electric Aircraft Engines and B. F. Goodrich test facilities. By using the same parent material, both sets of liners were identical to within the limits of material and fabrication variability. Baseline data were obtained in the normal incidence impedance tubes at NASA Langley and B. F. Goodrich. The results were found to compare extremely well. The samples were then tested in the grazing flow ducts of each of the four laboratories. Perhaps the most significant result of these comparisons is that the educed acoustic resistances for the liners used in this study increase as the mean flow profile is modified from uniform to 3-D shear. This realization has demonstrated the need for an frequency-dependent impedance eduction technique that incorporates 3-D shear flow and is efficient.

Jones, M. G.↗
NASA NTRS2018

Impact of Gaps in the NASA-ISRO SAR Mission Swath

The NASA-ISRO Synthetic Aperture Radar (NISAR) mission will carry L-band and S-band SAR instruments, each with a 240 km swath width. The L-band instrument has the capability to map the entire Earth’s land and ice covered surfaces from both ascending and descending orbit positions, continuously in an exact 12 day repeating cycle, given temporally dense (better than 6-day on average) sampling of Earth over the life of the mission. To achieve this swath coverage without loss of resolution or polarimetric capability, NISAR uses a reflector-feed based antenna system with scan-on-receive (“SweepSAR”) capability. One of the characteristics of SweepSAR is that the pulse repetition interval of the radar is shorter than the echo receive window for the 240 km swath. Therefore, transmit events occur during the receive window and the receivers must be blanked periodically, creating gaps in the coverage. For fixed pulse rate operations, these gaps are persistent strips of blanked ranges. NISAR is being designed to allow variation of the pulse rate in order to spread out these gaps throughout the synthetic aperture, but processing these variably-acquired data is more challenging and can lead to compromises in image quality. At the highest level NISAR places requirements on science measurements rather than image quality, so there is often a debate among science and engineering team members as to whether to operate with fixed pulse rates – leading to range strips consistently blank from cycle to cycle but with optimal image quality – or to vary the pulse rate, fill in the gaps, and live with degraded image quality. NISAR’s performance team has shown that science requirements can be met with the gaps. However, scientists are eager for maximum and coverage within a swath. A companion paper (Villano et al.) describes image quality for NISAR using a variable PRF approach, but does not go further to science requirements. This paper explores the issues when gaps are present in the swath due to fixed PRF operations.

Veeramachaneni, Chandini↗
DOE OSTI2023

New Insights from Legacy Seismic Data regarding Basalt Elevations and Variability on the Hanford Site

Migration of groundwater contaminants in the Gable Gap area of the Hanford Site in southeastern Washington State is strongly influenced by the distribution and permeability of basalts that lie beneath an unconfined aquifer. Locally, folding and faulting of the Columbia River Basalt associated with the Yakima fold and thrust belt followed by erosion due to the Lake Missoula floods resulted in a complex basalt surface that represents either an impermeable lower boundary to the unconfined aquifer system or localized regions of increased permeability that potentially promote communication between the unconfined aquifer system and deeper, confined aquifer systems. Paleo-channels carved into the basalt by floodwaters are thought to provide preferential flow paths for groundwater contaminants. In 2011, a seismic landstreamer campaign was carried out to image the basalt surface and produced pre-stack depth migrated p-wave reflection images. The reflection images identified two large troughs that may represent paleo-channels and several areas of possible faulting. Here, the streamer data are re-analyzed using refraction travel-time and Rayleigh wave dispersion analyses to obtain images of compressional and shear wave velocities within the suprabasalt sediment sections and the upper basalt surface. The combined interpretation of reflection and seismic velocity images shows complexity in the basalt velocity and elevation, which varies by 50 m or more within the study area. These results, along with other ongoing geophysical investigations, will be used to inform the site geologic model and potentially guide placement of future boreholes needed to quantify vertical flow between the confined and unconfined aquifers.

58 GEOSCIENCES↗
NASA NTRS1982

GRAVSAT error analysis by means of global spectral analyses of the marine geoid from SEASAT altimeter data

The geographical variability of short wavelength geoid power spectra (geoid roughness), was mapped for the world's oceans between latitudes 72 deg N and 72 deg S. A spectral analysis of SEASAT altimeter data, reduced to sea surface heights, was performed at 2 minute intervals for 15 consecutive days of the 3-day repeat orbit. The geoid roughness represented by these spectra for wavelengths shorter than about 220 km is separated from the total sea height variance and is displayed in the form of a global contour map. The global average geoid roughness is 32 cm RMS, varying from a high in excess of 2 m RMS near deep ocean trenches to a low of 2 cm RMS in the southeast Pacific near the East Pacific Rise. This average value agrees well with previous estimates based on gravimetry and GEOS-3 altimetry. In general, the smoothest areas in the marine geoid overlie relatively young seafloor adjacent mid-ocean spreading centers, where even short-wavelength topographic variations tend to be isostatically compensated.

Source record↗
NASA NTRS1982

A failure model for sealed nickel-cadmium batteries

A model has been developed to describe failure in electrochemical batteries. The model is based on the concept of the existence and subsequent growth of flaws which ultimately lead to battery failure. This model provides, in a natural way, for the statistical variability of lifetime data. The model as applied to the Crane data indicates that when the effects of temperature and depth of discharge are taken into account, the observed variability in lifetime data is due almost entirely to statistical variability inherent in the battery itself.

Fedors, R. F.↗
NASA NTRS1989

Measurements of NO(x) over the eastern Pacific Ocean and southwestern United States during the spring 1984 NASA GTE aircraft program

Measurements of NO, NO(x) (NO + NO2), O3, and CO are presented from seven aircraft flights made over the eastern Pacific Ocean and the southwestern United States in spring of 1984. The sampling region was characterized by large- and small-scale variability for all of the measurements, likely as a result of vigorous synoptic scale meteorology and the influence of tropopause folds. Median values for NO, NO(x), O3, and CO from the flights made over the ocean in the region of 5.8-7.6 km were 10 parts per trillion by volume (pptv), 32 pptv, 46 parts per billion by volume (ppbv), and 120 ppbv, respectively. Corresponding values from two flights made over the continent at similar altitudes were 16 pptv, 38 pptv, 42 ppbv, and 111 ppbv. There was a strong tendency for NO or NO(x) to be correlated positively with O3 and to be anticorrelated with dew-point/frost-point measurements. No significant overall correlation occurred between NO(x) and CO for the ocean data. The variability of NO(x) was such that regions of net destruction and regions of net production of O(3) were sampled both over the ocean and over the continent. However, in the middle free troposphere over the ocean, net O(3) destruction was predominant.

Ridley, B. A.↗
NASA NTRS1996

(abstract) Role of Long Equatorial Wave Reflection in the Low-Frequency Variability Observed During the TOPEX/POSEIDON Period: Data Analysis and Coupled Model Study

The analysis of TOPEX/POSEIDON sea level and ERS-1 zonal wind stress data gives evidence that first mode meridonal long Rossby waves fully reflected into Kelvin waves at the equatorial western Pacific boundary at different periods including the January-June 1994 period. The evolution of the conditions (zonal wind stress, sea surface temperature and sea level anomalies) in the central Pacific suggests that this reflection may have played a role in the reversal of cold to warm anomalies observed in the central Pacific in June-July 1994. To investigate the actual role of reflected Kelvin waves observed by TOPEX/POSEIDON, a simple ocean-atmosphere coupled model is designed. Starting from these initial conditions, several simulations are run for testing the role western bundary reflection evidenced in TOPEX/POSEIDON data. Coupled mechanisms are suggested to explain the low-frequency variability observed during this period.

Rossby waves Kelvin waves zonal wind stress TOPEX/↗
NASA NTRS2004

Spray Characteristics of a Hybrid Twin-Fluid Pressure-Swirl Atomizer

The spray performance of a fuel injection system applicable for use in main combustion chamber of an oxidizer-rich staged combustion (ORSC) cycles is presented. The experimental data reported here include mean drop size and drop size distribution, spray cone half-angle, and momentum rate (directly related to spray penetration). The maximum entropy formalism, MEF, method to predict drop size distribution is applied and compared to the experimental data. Geometric variables considered include the radius of the injector inlet orifice plate through which oxidizer flows (&) and the exposed length from the fuel inlet to the injector exit plane (L2). Operating conditions that were varied include the liquid mass flow rate and air mass flow rate. For orifices B and C there is a significant dependence of D3Z on both the air and liquid mass flow rates, as well as on L2. For the A orifice, the momentum rate of the air flow appears to exceed a threshold value above which a constant D32 is obtained. Using the MEF method, a semi-analytical process was developed to model the spray distribution using two input parameters (q = 0.4 and Dso). The momentum rate of the spray is directly related to the air and liquid mass flow rates. The cone half angle of the spray ranges from 25 to 17 degrees. The data resulting from this project will eventually be used to develop advanced rocket systems.

Durham, M. J.↗
NASA NTRS2001

Estimation of comprehensive forest variable sets from multiparameter SAR data over a large area with diverse species

Polarimetric and multifrequency data from the NASA/JPL airborne synthetic aperture radar (AIRSAR) have been used in a multi-tier estimation algorithm to calculate a comprehensive set of forest canopy properties including branch layer moisture and thickness, trunk density, trunk water content and diameter, trunk height, and subcanapy soil moisture. The estimation algorithm takes advantage of species-specific allometric relations, and is applied to a 100Km x 100Km area in the Canadian boreal region containing many different vegetation species types. The results show very good agreement with ground measurements taken at several focused and auxiliary study sites. This paper expands on the results reported in [1] and applies the algorithm on the regional scale.

variable estimation forestry multiparameter SAR↗
NASA NTRS1995

Temporal variation of meandering intensity and domain-wide lateral oscillations of the Gulf Stream

The path of the Gulf Stream exhibits two modes of variability: wavelike spatial meanders associated with instability processes and large-sale lateral shifts of the path presumably due to atmospheric forcing. The objectives of this study are to examine the temporal variation of the intensity of spatial meandering in the stream, to characterize large-scale lateral oscillations in the stream's path, and to study the correlation betwen these two dynamically distinct modes of variability. The data used for this analysis are path displacemets ofthe Gulf Stream between 75 deg and 60 deg W obtained from AVHRR-derived (Advanced Very High Resolution Radiometer) infrared images for the period April 1982 through December 1989. Meandering intensity, measured by the spatial root-mean-sqaure displacement of the stream path, displays a 9-month dominant periodicity which is persistent through the study period. The 9-month fluctuation in meandering intensity may be related to the interaction of Rosseby waves with the stream. Interannual variation of meandering intensity is also found to be significant, with meandering being mich more intense during 1985 than it was in 1987. Annual variation, however,is weak and not well-defined.The spatially averaged position of the stream, which reflects nonmeandering large-scale lateral oscillations of the stream path, is dominated by an annual cycle. On average, the mean position is farthest north in November and farthest south in April. The first empirical orthogonal function mode of the space-time path displacements represents lateral oscillatins that are in-phase over the space-time domain. Interannual oscillations are also observed and are found to be weaker than the annual oscillation. The eigenvalue of the first mode indicates that about 21.5% of the total space-time variability of the stream path can be attibuted to domain-wide lateral oscillation. The correlation between meandering intensity and domain-wide lateral oscillations is very weak.

Lee, Tong↗
DOE OSTI2024

Comparative Performance of Three Eye-Tracking Devices in Detection of Mild Traumatic Brain Injury in Acute Versus Chronic Subject Populations

ABSTRACT Introduction Presently, traumatic brain injury (TBI) triage in field settings relies on symptom-based screening tools such as the updated Military Acute Concussion Evaluation. Objective eye-tracking may provide an alternative means of neurotrauma screening due to sensitivity to neurotrauma brain-health changes. Previously, the US Army Medical Research and Development Command Non-Invasive NeuroAssessment Devices (NINAD) Integrated Product Team identified 3 commercially available eye-tracking devices (SyncThink EYE-SYNC, Oculogica EyeBOX, NeuroKinetics IPAS) as meeting criteria toward being operationally effective in the detection of TBI in service members. We compared these devices to assess their relative performance in the classification of mild traumatic brain injury (mTBI) subjects versus normal healthy controls. Materials and Methods Participants 18 to 45 years of age were assigned to Acute mTBI, Chronic mTBI, or Control group per study criteria. Each completed a TBI assessment protocol with all 3 devices counterbalanced across participants. Acute mTBI participants were tested within 72 hours following injury whereas time since last injury for the Chronic mTBI group ranged from months to years. Discriminant analysis was undertaken to determine device classification performance in separating TBI subjects from controls. Area Under the Curves (AUCs) were calculated and used to compare the accuracy of device performance. Device-related factors including data quality, the need to repeat tests, and technical issues experienced were aggregated for reporting. Results A total of 63 participants were recruited as Acute mTBI subjects, 34 as Chronic mTBI subjects, and 119 participants without history of TBI as controls. To maximize outcomes, poorer quality data were excluded from analysis using specific criteria where possible. Final analysis utilized 49 (43 male/6 female, mean [x̅] age = 24.3 years, SD [s] = 5.1) Acute mTBI subjects, and 34 (33 male/1 female, x̅ age = 38.8 years, s = 3.9) Chronic mTBI subjects were age- and gender-matched as closely as possible with Control subjects. AUCs obtained with 80% of total dataset ranged from 0.690 to 0.950 for the Acute Group and from 0.753 to 0.811 for the Chronic mTBI group. Validation with the remaining 20% of dataset produced AUCs ranging from 0.600 to 0.750 for Acute mTBI group and 0.490 to 0.571 for the Chronic mTBI group. Conclusions Potential eye-tracking detection of mTBI, per training model outcomes, ranged from acceptable to excellent for the Acute mTBI group; however, it was less consistent for the Chronic mTBI group. The self-imposed targeted performance (AUC of 0.850) appears achievable, but further device improvements and research are necessary. Discriminant analysis models differed for the Acute versus Chronic mTBI groups, suggesting performance differences in eye-tracking. Although eye-tracking demonstrated sensitivity in the Chronic group, a more rigorous and/or longitudinal study design is required to evaluate this observation. mTBI injuries were not controlled for this study, potentially reducing eye-tracking assessment sensitivity. Overall, these findings indicate that while eye-tracking remains a viable means of mTBI screening, device-specific variability in data quality, length of testing, and ease of use must be addressed to achieve NINAD objectives and DoD implementation.

General & Internal Medicine↗
NASA NTRS1999

Characterization of the Heat Extraction Capability of a Compliant, Sliding, Thermal Interface for Use in a High Temperature, Vacuum Microgravity Furnace

Much of the material science gained in microgravity research requires processing a sample in a high performance furnace. One such furnace currently being designed is the Quench Module Insert (QMI). The Principle Investigators, for whom the furnace is proposed, require high temperature gradients in their cylindrical samples to achieve the science objectives. One of the components critical to achieving high sample axial temperature gradients in the Quench Module Insert is a high performance cold zone to extract the heat from the sample. This cold zone employs a compliant, sliding thermal interface based on a Vel-Therm felt. This felt provides a conductive path between the Sample Cartridge Assembly (SCA) exterior surface and the interior surface of the water cooled chill block while allowing movement of the sample relative to the chill block. The Vel-Therm felt is composed of long polymer-based fibers affixed to a thin flexible substrate layer. The fibers are oriented perpendicular to this substrate giving the felt the appearance of a velvet fabric. The Vel-Therm felt heat extraction capability was quantified in earlier tests performed in an inert gas environment. The current activity, described in this paper, is intended to characterize the extraction capability of Vel-Therm felt in a vacuum environment similar to the QMI environment. This testing is necessary to quantify the thermal performance of the Vel-Therm felt and the sensitivity of that performance to key variables. The data derived from these tests will be incorporated into the current thermal models to improve the quality of the models and reduce uncertainty of the analytical results. In addition, the data will be used to help select the appropriate Vel-Therm felt and set proper operating limits as well as assess the performance range of the furnace. The objective of this test is to measure the heat extraction rate of the Vel-Therm felt as specified by the effective heat transfer coefficient. Therefore, the test setup was designed to force the bulk of the heat transfer through the area where the Vel-Therm felt was applied. A heat source, consisting of a ceramic heating element encased in a Copper (Cu) housing is mounted on four isolated support rods. A 6-layer molybdenum radiation shield is used to insulate against heat loss from the heater and prevent heat exchange between the hot and cold sides of the test apparatus. The Vel-Therm felt is affixed to the surface of the cold sink, a water-cooled Cu chill block. An adjustable plate supports and isolates the cold sink from above and is used to control the amount of the deflection of the Vel- Therm when in contact with the Cu heating element housing. The primary means of establishing the power being conducted through the felt is to measure the energy being transferred to the water passing through the chill block. Analysis was performed to support the assumption that the source and sink surfaces were approximately isothermal under the specific test conditions. As a check on the amount of power passing through the felt, the power supplied to the heater was also measured. Thermocouples were strategically located throughout the test apparatus for measurement purposes. A bell jar was lowered over the assembly to impose vacuum conditions. Currently, variables tested have been fiber compression and fiber type and surface temperatures (both the hot and cold side temperatures are hypothesized to be important to the performance of the Vel-Therm.) Selected runs were repeated to ensure consistency and repeatability. Results obtained thus far reveal that Vel-Therm performance is significantly degraded by fibers being exposed to high compression. It also shows that performance is somewhat negatively impacted by previous compression, thereby, raising the question of repeatability. In addition, early results show a significant dependence on temperature. A computer aided mathematical analysis of the test setup is ongoing. The results will be correlated to actual results. The correlation will examine such details as parasitic loses, conduction down the power leads and many other concerns.

Bellomy-Ezell, Jenny↗
DOE OSTI2024

A decade of insights: Delving into calendar aging trends and implications

Lithium-ion batteries remain at rest for extended periods and experience calendar aging. Although lithium-ion batteries are expected to perform for over 10 years at room temperature, long-term calendar aging data are seldom reported over such timescales. We present a dataset from 232 commercial cells across eight cell types and five manufacturers that underwent calendar aging across various temperatures and states of charge (SOCs) for up to 13 years. We analyze calendar aging across these conditions by tracking capacity loss and resistance growth as the cells degrade. This dataset is used to validate simple models, primarily the Arrhenius law and the power law, which explain the temperature and storage time on calendar aging. Certain applications of Arrhenius and power law fail to describe the dependence of capacity loss on temperature and resistance growth on storage time. Through this dataset, we demonstrate the complexity of calendar aging and the challenges in reducing trends into phenomenological models.

25 ENERGY STORAGE↗
NASA NTRS1994

Spectropolarimetric variability in OB stars

Data from the Wisconsin spectropolarimetric monitoring program provide information about the polarimetric variability of numerous types of stars. Examining the data that exist thus far, we find, not surprisingly, that many OB stars, especially OB supergiants and Be stars, are polarimetric variables. Be stars show the most extreme variable as a class. Results from the Be star pi Aqr are presented which illustrate the dramatic polarimetric variability that such stars can exhibit. Contemporaneous IUE data show that the development of low velocity discrete absorption components in the UV wind lines may be associated with the onset of polarimetric outbursts. These preliminary findings add further support to the picture that winds from hot stars are non-homogeneous and variable.

Bjorkman, K. S.↗
DOE OSTI2021

Subfield crop yields and temporal stability in thousands of US Midwest fields

Understanding subfield crop yields and temporal stability is critical to better manage crops. Several algorithms have proposed to study within-field temporal variability but they were mostly limited to few fields. In this study, a large dataset composed of 5520 yield maps from 768 fields provided by farmers was used to investigate the influence of subfield yield distribution skewness on temporal variability. The data are used to test two intuitive algorithms for mapping stability: one based on standard deviation and the second based on pixel ranking and percentiles. The analysis of yield monitor data indicates that yield distribution is asymmetric, and it tends to be negatively skewed (p < 0.05) for all of the four crops analyzed, meaning that low yielding areas are lower in frequency but cover a larger range of low values. The mean yield difference between the pixels classified as high-and-stable and the pixels classified as low-and-stable was 1.04 Mg ha –1 for maize, 0.39 Mg ha –1 for cotton, 0.34 Mg ha –1 for soybean, and 0.59 Mg ha —1 for wheat. The yield of the unstable zones was similar to the pixels classified as low-and-stable by the standard deviation algorithm, whereas the two-way outlier algorithm did not exhibit this bias. Furthermore, the increase in the number years of yield maps available induced a modest but significant increase in the certainty of stability classifications, and the proportion of unstable pixels increased with the precipitation heterogeneity between the years comprising the yield maps.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Late Holocene history of Tokotan Lake (Kuril Archipelago, Russian Far East): The use of lacustrine records for paleoclimatic reconstructions from geologically dynamic settings

A high-resolution, multiproxy analysis of a core from Tokotan Lake, Urup Island, illustrates the complex paleoenvironmental signals that can be preserved in sedimentary deposits from geologically active areas, such as the Kuril Archipelago. Diatom and geochemical analyses of the Tokotan core suggest a shallowing and lessening of the lake area over the last ~3450 cal BP. Without other proxies, the record could be interpreted as showing a general decrease in precipitation over the Late Holocene. However, palynological data indicate no change in vegetation, thereby implying no significant climatic variation. Neither of these paleoclimatic interpretations agrees with Late Holocene reconstructions from the Kuril Archipelago or the Russian mainland. Paleomagnetic data imply variable sediment sources during the lake's history, indicating alterations within the Tokotan catchment (e.g., shifts in gradients or sediment loads in the inflowing streams). Such changes would be particularly important in the Shabalina River, which today has formed a partial dam across the lake's outlet. Here, the results of the Tokotan study indicate that other factors (e.g., volcanism, seismic activity, sea-level changes) rather than climate were more probable determinants of the Late Holocene lake record. Given the geologic dynamism of the region, it is perhaps not surprising that paleo-records from the Kuril Islands display an inconsistency in the numbers and/or duration of proposed Holocene climatic oscillations, underscoring the importance of multiproxy investigations in areas that are or have been geologically dynamic.

58 GEOSCIENCES↗
DOE OSTI2021

Mechanistic Pathways for N 2 O Elimination from trans -R 3 Sn-O-N=N-O-SnR 3 and for Reversible Binding of CO 2 to R 3 Sn-O-SnR 3 (R = Ph, Cy)

The rate and mechanism of the elimination of N 2 O from trans-R 3 Sn-O-N=N-O-SnR 3 (R = Ph ( 1 Ph ) and R = Cy ( 1 Cy )) to form R 3 Sn-O-SnR 3 (R = Ph ( 2 Ph ) and R = Cy ( 2 Cy )) have been studied using both NMR and IR techniques to monitor the reactions in the temperature range of 39–79 °C in C 6 D 6 . Activation parameters for this reaction are ΔH ‡ = 15.8 ± 2.0 kcal·mol –1 and ΔS ‡ = –28.5 ± 5 cal·mol –1 ·K –1 for 1 Ph and ΔH ‡ = 22.7 ± 2.5 kcal·mol –1 and ΔS ‡ = –12.4 ± 6 cal·mol –1 ·K –1 for 1 Cy . Addition of O 2 , CO 2 , N 2 O, or PPh 3 to sealed tube NMR experiments did not alter in a detectable way the rate or product distribution of the reactions. Computational DFT studies of elimination of hyponitrite from trans-Me 3 Sn-O-N=N-O-SnMe 3 ( 1 Me ) yield a mechanism involving initial migration of the R 3 Sn group from O to N passing through a marginally stable intermediate product and subsequent N 2 O elimination. Reactions of 1 Ph with protic acids HX are rapid and lead to formation of R 3 SnX and trans-H 2 N 2 O 2 . Reaction of 1 Ph with the metal radical •Cr(CO) 3 C 5 Me 5 at low concentrations results in rapid evolution of N 2 O. At higher •Cr(CO) 3 C 5 Me 5 concentrations, evolution of CO 2 rather than N 2 O is observed. Addition of 1 atm or less CO 2 to benzene or toluene solutions of 2 Ph and 2 Cy resulted in very rapid reaction to form the corresponding carbonates R 3 Sn-O-C(=O)-O-SnR 3 (R = Ph ( 3 Ph ) and R = Cy ( 3 Cy )) at room temperature. Evacuation results in fast loss of bound CO 2 and regeneration of 2 Ph and 2 Cy . Variable temperature data for formation of 3 Cy yield ΔH o = –8.7 ± 0.6 kcal·mol –1 , ΔS o = –17.1 ± 2.0 cal·mol –1 ·K –1 , and ΔG o 298K = –3.6 ± 1.2 kcal·mol –1 . Furthermore, DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗