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At least 217 records · Page 12

Probing High-Temperature Amine Chemistry: Is the Reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 Important?

The reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 (R1) has been identified as a key step to explain experimental results for pyrolysis and oxidation of ammonia. However, no direct experimental or theoretical evidence for the reaction has been reported. In the present work, the reaction was studied by ab initio theory and by reinterpretation of experimental data. We could not locate a transition state for R1 occurring as a direct process, but alternative mechanisms yielded an upper bound to k 1 of 1.5 × 10 13 exp(–58.9 kcal mol –1 /RT) cm 3 mol –1 s –1 over 1000–2500 K, several orders of magnitude lower than values applied in modeling. Consistent with the theoretical work, re-evaluation of NH 3 pyrolysis data supported a very low value of k 1 . However, this finding opens up a novel unresolved issue. Current kinetic models cannot capture the NH 3 oxidation behavior in a number of laminar flow reactor and jet-stirred reactor experiments without adopting an improbably high value for k 1 . Furthermore, important oxidation steps might be underestimated or missing from mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dehydration kinetics of nanoconfined water in beryl probed by high temperature single crystal synchrotron X-ray diffraction

Understanding changes in material properties through external stimuli plays a key role in validating the expected performance of materials and engineering material properties in a controlled manner. Here, we introduce a fundamental protocol to deduce dehydration reactions kinetics of water confined in nanopore channels, with the cyclosilicate beryl as the scaffold of interest, using time-resolved synchrotron X-ray diffraction (SXRD), in the temperature interval of 298–1038 K. The temperature-dependent intensity (I) of the strongest reflection (112) was used as the crystallite variable. An estimation of an isobaric thermal crystallite coefficient, k, analogous with the isobaric thermal expansion coefficient, established the rate of relative crystallization as a function of temperature, $\frac{∂I}{∂T}$. A plot of lnk and $\frac{1}{T}$ gives rise to two kinetic steps, indicating a slow dehydration stage up to ~ 700 K and a fast dehydration stage up to the investigated temperature 1038 K. The crystal structure of beryl determined up to 1038 K, in temperature increment as small as 10 K, indicates the presence of channel ions Na and Fe and a gradual decrease of water upon heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallization of nanopore-confined imidazolium ionic liquids probed by temperature-resolved in situ grazing-incidence wide angle X-ray scattering (GIWAXS)

The crystallization behavior of ionic liquids (ILs) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF 6 ] and chloride [Cl] is investigated upon confinement in 2.3 or 8.2 nm diameter silica nanopore arrays, along with the effects of covalently modifying the pore walls with 1-(3-trimethoxysilylpropyl)3-methylimidazolium [TMS-MIM] + groups. In situ grazing-incidence wide angle x-ray scattering (GIWAXS) is performed during heating from as low as -110 °C to room temperature. Partially ordered “nanodomains” are observed in both ILs in the bulk molten state, but they are disrupted by nanoconfinement. Melting point depression consistent with capillary effects is observed for [BMIM][PF 6 ] in 2.3 nm pores. However, the melting point is elevated for [BMIM][PF 6 ] in 8.2 nm pores, which provide sufficient space to stabilize the crystalline phase. For [BMIM][Cl], crystallization is observed only in 8.2 nm bare silica pores, but the melting point is severely depressed. Tethering with IL-like [TMS-MIM + ] also promotes the crystallization of [BMIM][PF 6 ], resulting in elevated melting points. The combined effects of a larger pore size and pore surface tethering on [BMIM][PF 6 ] result in a single stable crystal phase that persists from -140 °C to 25 °C (vs. the bulk melting point of -11 °C). These results show that when ILs are used in confined systems, complex crystallization behavior can emerge depending on the counterion, pore size, and surface modification that require consideration of ion layering in the confined space in addition to surface free energy effects.

He, Yuxin [University of Kentucky, Lexington, KY (↗

A probe for measuring temperature and pressure at the same points in a gas stream

Design features and characteristics of a means for measuring total temperature and total pressure at a single point in a gas stream are presented. A rake that provides five such combination measurements is described. Experimental data are included for the aerodynamic recovery and time response of the temperature sensor and for the flow-angle sensitivity of both the temperature and pressure sensors. Data were obtained over a subsonic Mach number range of 0.3 to 0.9 as well as at a Mach number of 1.4.

Krause, L. N.↗

Acoustical Measurement Of Furnace Temperatures

Simple probes withstand severe conditions, yet give spatially-resolved temperature readings. Prototype acoustical system developed to measure temperatures from ambient to 1,800 degree F in such structures as large industrial lime kilns and recovery-boiler furnaces. Pulses of sound reflected from obstructions in sensing tube. Speed of sound and temperature in each segment deduced from travel times of pulses.

Parthasarathy, Shakkottai↗

The calibration and operation of a constant-temperature crossed-wire probe in supersonic flow

The calibration and operation of a constant-temperature crossed-wire probe in supersonic flow is considered. Crossed-wire probes offer considerable advantages over single, inclined wires: the kinematic shear stress can be derived from a single point measurement; the rms quantities can be derived from the same measurement, and the instantaneous quantities can be obtained as a continuous function of time. However, using a crossed-wire probe in supersonic flow is subject to the following practical difficulties: the problem of flow interference, where the shock waves from one wire and its supports interfere with the flow over the other wire; the necessity for high frequency response to resolve the spectral content, and the sensitivity of the results to small changes in the calibration constants. In the present contribution, each of these problems is addressed. Practical solutions are suggested, and some encouraging results are presented.

Fernando, E. M.↗

Thermocouples measure very-hot gas temperatures

Thermocouple probe incorporates small jet of inert gas to cool thermocouple. To measure gas temperatures, cooling jet is turned off momentarily, allowing thermocouple to heat up to near its melting point, then cooling is reapplied. Heating curve is recorded by high speed digital system. Computing system extrapolates final temperature thermocouple would have attained.

Glawe, G. E.↗

Flexible Cryogenic Temperature and Liquid-Level Probes

Lightweight, flexible probes have been developed for measuring temperatures at multiple locations in tanks that contain possibly pressurized cryogenic fluids. If the fluid in a given tank is subcritical (that is, if it consists of a liquid and its vapor), then in one of two modes of operation, the temperature measurements made by a probe of this type can be used to deduce the approximate level of the liquid. The temperature sensors are silicon diodes located at intervals along a probe. If the probe is to be used to measure a temperature gradient along a given axis in the tank, then the probe must be mounted along that axis. In the temperature-measurement mode, a constant small electric current is applied to each diode and the voltage across the diode a known function of the current and temperature is measured as an indication of its temperature. For the purpose of this measurement, small electric current signifies a current that is not large enough to cause a significant increase in the measured temperature. More specifically, the probe design calls for a current of 10 A, which, in the cryogenic temperature range of interest, generates heat at a rate of only about 0.01 mW per diode. In the liquid-level-sensing mode, one applies a larger current (30 mA) to each diode so as to heat each diode appreciably (with a power of about 36 mW in the temperature range of interest). Because the liquid cools the diode faster than does the vapor, the temperature of the diode is less when the diode is immersed in the liquid than when it is above the surface of the liquid. Thus, the temperature (voltage) reading from each diode can be used to determine whether the liquid level is above or below the diode, and one can deduce that the liquid level lies between two adjacent diodes, the lower one of which reads a significantly lower temperature. The aforementioned techniques for measuring temperature and deducing liquid level are not new. What is new here are the designs of the probes and of associated external electronic circuitry. In each probe, the diodes and the lead wires are embedded in a strong, lightweight, flexible polyimide strip. Each probe is constructed as an integral unit that includes a multipin input/output plug or socket for solderless connection of the lead wires to the external circuitry. The polyimide strip includes mounting tabs with holes that can accommodate rivets, screws, or other fasteners. Alternatively, a probe can be mounted by use of an epoxy. A probe can be manufactured to almost any length or width, and the diodes can be embedded at almost any desired location along and across the polyimide strip. In designing a probe for a specific application, one seeks a compromise between (1) minimizing the number of diodes in order to minimize the complexity of input/output connections and external electronic circuitry while (2) using enough diodes to obtain the required precision. Optionally, to minimize spurious heating of the cryogenic fluid, the external circuitry can be designed to apply power to the probe only during brief measurement intervals. Assuming that the external circuitry is maintained at a steady temperature, a power-on interval of only a few seconds is sufficient to obtain accurate data on temperatures and/or the height of the liquid/vapor interface.

Haberbusch, Mark↗

Flexible Cryogenic Temperature and Liquid-Level Probes

Lightweight, flexible probes have been developed for measuring temperatures at multiple locations in tanks that contain possibly pressurized cryogenic fluids. If the fluid in a given tank is subcritical (that is, if it consists of a liquid and its vapor), then in one of two modes of operation, the temperature measurements made by a probe of this type can be used to deduce the approximate level of the liquid. The temperature sensors are silicon diodes located at intervals along a probe. If the probe is to be used to measure a temperature gradient along a given axis in the tank, then the probe must be mounted along that axis. In the non-liquid-level-sensing temperature-measurement mode, a constant small electric current is applied to each diode and the voltage across the diode . a known function of the current and temperature . is measured as an indication of its temperature. For the purpose of this measurement, "small electric current" signifies a current that is not large enough to cause a significant increase in the measured temperature. More specifically, the probe design calls for a current of 10 A, which, in the cryogenic temperature range of interest, generates heat at a rate of only about 0.01 mW per diode. In the liquid-level-sensing mode, one applies a larger current (30 mA) to each diode so as to heat each diode appreciably (with a power of about 36 mW in the temperature range of interest). Because the liquid cools the diode faster than does the vapor, the temperature of the diode is less when diode is immersed in the liquid than when it is above the surface of the liquid. Thus, the temperature (voltage) reading from each diode can be used to determine whether the liquid level is above or below the diode, and one can deduce that the liquid level lies between two adjacent diodes, the lower one of which reads a significantly lower temperature. The aforementioned techniques for measuring temperature and deducing liquid level are not new. What is new here are the designs of the probes and of associated external electronic circuitry. In each probe, the diodes and the lead wires are embedded in a strong, lightweight, flexible polyimide strip. Each probe is constructed as an integral unit that includes a multipin input/output plug or socket for solderless connection of the lead wires to the external circuitry. The polyimide strip includes mounting tabs with holes that can accommodate rivets, screws, or other fasteners. Alternatively, a probe can be mounted by use of an epoxy. A probe can be manufactured to almost any length or width, and the diodes can be embedded at almost any desired locations along and across the polyimide strip. In designing a probe for a specific application, one seeks a compromise between (1) minimizing the number of diodes in order to minimize the complexity of input/output connections and external electronic circuitry while (2) using enough diodes to obtain the required precision. Optionally, to minimize spurious heating of the cryogenic fluid, the external circuitry can be designed to apply power to the probe only during brief measurement intervals. Assuming that the external circuitry is maintained at a steady temperature, a power-on interval of only a few seconds is sufficient to obtain accurate data on temperatures and/or the height of the liquid/vapor interface.

Haberbusch, Mark↗

Continuous snow depth, ground interface temperature and shallow soil temperature measurements from 2021-10-1 to 2022-6-14, Seward Peninsula, Alaska

The dataset contains co-located snow depth, ground interface temperature, and shallow soil temperature measured at 98 discrete locations in a watershed located along the Nome-Teller road at mile marker 27 (referred to as T27), and at 53 discrete locations on a hillslope located along the Kougarok road at mile marker 64 (referred to as K64), in Seward Peninsula, Alaska. The dataset aims to understand the local heterogeneity of snow depth, snow temperature, and soil temperature dynamics and their interactions in a discontinuous permafrost region. The dataset is also valuable to train and evaluate machine learning and physical models to predict snow depth or the impact of snow depth on ground surface temperature. At each location, temperatures above and below the ground surface were measured by a pair of vertically deployed distributed temperature profiling probes designed based on Dafflon et al (2022). The probes have high precision temperature sensors spaced at 5 or 10 cm. The mean daily snow depth was estimated by identifying the pair of consecutive sensors with maximum drop of daily temperature high-frequency fluctuations. The ground interface temperature was measured by the sensor located 1-5 cm above the ground surface at 15-minute intervals. The shallow soil temperature was measured by the sensor located 1-5 cm below the ground surface at 15-minute intervals. The dataset includes a description of the probe locations in the "Probe_locations_*.csv" file and the 3 data files (Snow_depths_*.csv, Ground_interface_temperatures_*.csv, Shallow_soil_temperatures_*.csv). * is either T27 or K64, which are the two study sites. In each data file, each column corresponds to a measurement location. Metadata files include data descriptions (_dd.csv) for tabular data. All included files are listed and described in xxxx_flmd.csv. A more detailed description of data processing, along with an updated dataset incorporating multiple seasons and improved snow depth estimation is available at https://doi.org/10.15485/2480365 (Wang et al., 2025a, Wang et al., 2025b).The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Active Layer Depth and Permafrost Temperatures at the Teller 47 Field Site, Seward Peninsula, Alaska, 2022

With extreme climate warming in the Arctic, there is increasing focus on mapping permafrost stability and improving understanding of the impacts of thawing permafrost. Summer active layer depths and temperatures at the top of the permafrost were collected at the Teller 47 field site on the Seward Peninsula, Alaska to better understand permafrost thermal state in areas of discontinuous permafrost. Measurements were taken between August 14th and August 20th, 2022. Active layer depths were measured with a 120 cm thaw probe, and temperature measurements were taken with a SpotOn Temperature probe at the top of permafrost and at a maximum depth of XYZ, when no near-surface permafrost (within 120 cm of the surface) was present. Measurements were co-located with ground surface displacement measurements, which can be found in the associated dataset, NGA254. Precise location data were collected at each observation point using a GNSS RTK GPS unit. This dataset contains a *.csv file of permafrost temperature and active layer depths and a *.kml file of measurement locations.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy’s Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy’s Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗