Communication: H-atom reactivity as a function of temperature in solid parahydrogen: The H + N2O reaction

NASA Astrophysics Data System (ADS)

Mutunga, Fredrick M.; Follett, Shelby E.; Anderson, David T.

2013-10-01

We present low temperature kinetic measurements for the H + N2O association reaction in solid parahydrogen (pH2) at liquid helium temperatures (1-5 K). We synthesize 15N218O doped pH2 solids via rapid vapor deposition onto an optical substrate attached to the cold tip of a liquid helium bath cryostat. We then subject the solids to short duration 193 nm irradiations to generate H-atoms produced as byproducts of the in situ N2O photodissociation, and monitor the subsequent reaction kinetics using rapid scan FTIR. For reactions initiated in solid pH2 at 4.3 K we observe little to no reaction; however, if we then slowly reduce the temperature of the solid we observe an abrupt onset to the H + N2O → cis-HNNO reaction at temperatures below 2.4 K. This abrupt change in the reaction kinetics is fully reversible as the temperature of the solid pH2 is repeatedly cycled. We speculate that the observed non-Arrhenius behavior (negative activation energy) is related to the stability of the pre-reactive complex between the H-atom and 15N218O reagents.

Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

PubMed Central

Yang, Jingbin; Li, Dongxu; Fang, Yuan

2017-01-01

C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

Diode laser measurements of linestrength and temperature-dependent lineshape parameters of H2O-, CO2-, and N2-perturbed H2O transitions near 2474 and 2482 nm

NASA Astrophysics Data System (ADS)

Goldenstein, Christopher S.; Jeffries, Jay B.; Hanson, Ronald K.

2013-11-01

Absorption lineshapes for two unresolved H2O doublets near 4029.52 and 4041.92 cm-1 were measured at high-resolution in a heated static cell using two distributed-feedback diode lasers. Measurements were acquired for H2O, CO2, and N2 perturbers over a temperature and pressure range of 650-1325 K and 2-760 Torr, respectively. Strong collisional narrowing effects were observed in CO2 and N2, but not in pure H2O. The Galatry profile was used to infer collisional-broadening and -narrowing coefficients and their respective temperature dependence for CO2 and N2 perturbers. The collisional-broadening and -narrowing coefficients for CO2 perturbers were found to decrease with increasing temperature in a similar manner. For N2 perturbers, the collisional-broadening coefficients increased with temperature while the collisional-narrowing coefficients decreased with increasing temperature. Self-broadening coefficients were inferred from Voigt profile fits and are compared with HITEMP 2010. The linestrengths of 17 H2O transitions are also reported.

Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability.

PubMed

Liu, Lianjun; Zhao, Cunyu; Zhao, Huilei; Pitts, Daniel; Li, Ying

2013-05-07

A novel MgO-patched TiO2 microsphere photocatalyst demonstrated 10 times higher activity toward CO production from CO2 photoreduction with H2O vapor, when the reaction temperature increased from 50 to 150 °C. The catalytic performance of hybrid MgO-TiO2 was much more stable than TiO2, particularly at a higher temperature, likely due to easier desorption of reaction intermediates and the enhanced CO2 adsorption by MgO.

UV-activated ZnO films on a flexible substrate for room temperature O2 and H2O sensing.

PubMed

Jacobs, Christopher B; Maksov, Artem B; Muckley, Eric S; Collins, Liam; Mahjouri-Samani, Masoud; Ievlev, Anton; Rouleau, Christopher M; Moon, Ji-Won; Graham, David E; Sumpter, Bobby G; Ivanov, Ilia N

2017-07-20

We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2 O. We propose that the distinctive responses to O 2 and H 2 O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2 O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O 2 and H 2 O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2 O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2 O at low temperature.

Single-ended mid-infrared laser-absorption sensor for simultaneous in situ measurements of H₂O, CO₂, CO, and temperature in combustion flows.

PubMed

Peng, Wen Yu; Goldenstein, Christopher S; Mitchell Spearrin, R; Jeffries, Jay B; Hanson, Ronald K

2016-11-20

The development and demonstration of a four-color single-ended mid-infrared tunable laser-absorption sensor for simultaneous measurements of H₂O, CO₂, CO, and temperature in combustion flows is described. This sensor operates by transmitting laser light through a single optical port and measuring the backscattered radiation from within the combustion device. Scanned-wavelength-modulation spectroscopy with second-harmonic detection and first-harmonic normalization (scanned-WMS-2f/1f) was used to account for variable signal collection and nonabsorption losses in the harsh environment. Two tunable diode lasers operating near 2551 and 2482 nm were utilized to measure H₂O concentration and temperature, while an interband cascade laser near 4176 nm and a quantum cascade laser near 4865 nm were used for measuring CO₂ and CO, respectively. The lasers were modulated at either 90 or 112 kHz and scanned across the peaks of their respective absorption features at 1 kHz, leading to a measurement rate of 2 kHz. A hybrid demultiplexing strategy involving both spectral filtering and frequency-domain demodulation was used to decouple the backscattered radiation into its constituent signals. Demonstration measurements were made in the exhaust of a laboratory-scale laminar methane-air flat-flame burner at atmospheric pressure and equivalence ratios ranging from 0.7 to 1.2. A stainless steel reflective plate was placed 0.78 cm away from the sensor head within the combustion exhaust, leading to a total absorption path length of 1.56 cm. Detection limits of 1.4% H₂O, 0.6% CO₂, and 0.4% CO by mole were reported. To the best of the authors' knowledge, this work represents the first demonstration of a mid-infrared laser-absorption sensor using a single-ended architecture in combustion flows.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

PubMed

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-27

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.

Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

DOE PAGES

Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.; ...

2017-07-20

Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

Single diode laser sensor for wide-range H2O temperature measurements.

PubMed

Gharavi, Mohammadreza; Buckley, Steven G

2004-04-01

A single diode laser absorption sensor (near 1477 nm) useful for simultaneous temperature and H2O concentration measurements is developed. The diode laser tunes approximately 1.2 cm(-1) over three H2O absorption transitions in each measurement. The line strengths of the transitions are measured over a temperature range from 468 to 977 K, based on high-resolution absorption measurements in a heated static cell. The results indicate that the selected transitions are suitable for sensitive temperature measurements in atmospheric pressure combustion systems using absorption line ratios. Comparing the results with HITRAN 96 data, it appears that these transitions will be sensitive over a wide range of temperatures (450-2000 K), suggesting applicability for combustion measurements.

Plasmaspheric H+, He+, O+, He++, and O++ Densities and Temperatures

NASA Technical Reports Server (NTRS)

Gallagher, D. L.; Craven, P. D.; Comfort H.

2013-01-01

Thermal plasmaspheric densities and temperatures for five ion species have recently become available, even though these quantities were derived some time ago from the Retarding Ion Mass Spectrometer onboard the Dynamics Explorer 1 satellite over the years 1981-1984. The quantitative properties will be presented. Densities are found to have one behavior with lessor statistical variation below about L=2 and another with much greater variability above that Lshell. Temperatures also have a behavior difference between low and higher L-values. The density ratio He++/H+ is the best behaved with values of about 0.2% that slightly increase with increasing L. Unlike the He+/H+ density ratio that on average decreases with increasing Lvalue, the O+/H+ and O++/H+ density ratios have decreasing values below about L=2 and increasing average ratios at higher L-values. Hydrogen ion temperatures range from about 0.2 eV to several 10s of eV for a few measurements, although the bulk of the observations are of temperatures below 3 eV, again increasing with L-value. The temperature ratios of He+/H+ are tightly ordered around 1.0 except for the middle plasmasphere between L=3.5 and 4.5 where He+ temperatures can be significantly higher. The temperatures of He++, O+, and O++ are consistently higher than H+.

Plasmaspheric H+, He+, He++, O+, and O++ Densities and Temperatures

NASA Technical Reports Server (NTRS)

Gallagher, G. L.; Craven, P. D.; Comfort, R. H.

2013-01-01

Thermal plasmaspheric densities and temperatures for five ion species have recently become available, even though these quantities were derived some time ago from the Retarding Ion Mass Spectrometer onboard the Dynamics Explorer 1 satellite over the years 1981-1984. The quantitative properties will be presented. Densities are found to have one behavior with lessor statistical variation below about L=2 and another with much greater variability above that Lshell. Temperatures also have a behavior difference between low and higher L-values. The density ratio He++/H+ is the best behaved with values of about 0.2% that slightly increase with increasing L. Unlike the He+/H+ density ratio that on average decreases with increasing Lvalue, the O+/H+ and O++/H+ density ratios have decreasing values below about L=2 and increasing average ratios at higher L-values. Hydrogen ion temperatures range from about 0.2 eV to several 10s of eV for a few measurements, although the bulk of the observations are of temperatures below 3 eV, again increasing with L-value. The temperature ratios of He+/H+ are tightly ordered around 1.0 except for the middle plasmasphere between L=3.5 and 4.5 where He+ temperatures can be significantly higher. The temperatures of He++, O+, and O++ are consistently higher than H+.

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

PubMed Central

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

Chip-to-chip SnO2 nanowire network sensors for room temperature H2 detection

NASA Astrophysics Data System (ADS)

Köck, A.; Brunet, E.; Mutinati, G. C.; Maier, T.; Steinhauer, S.

2012-06-01

The employment of nanowires is a very powerful strategy to improve gas sensor performance. We demonstrate a gas sensor device, which is based on silicon chip-to-chip synthesis of ultralong tin oxide (SnO2) nanowires. The sensor device employs an interconnected SnO2 nanowire network configuration, which exhibits a huge surface-to-volume ratio and provides full access of the target gas to the nanowires. The chip-to-chip SnO2 nanowire device is able to detect a H2 concentration of only 20 ppm in synthetic air with ~ 60% relative humidity at room temperature. At an operating temperature of 300°C a concentration of 50 ppm H2 results in a sensitivity of 5%. At this elevated temperature the sensor shows a linear response in a concentration range between 10 ppm and 100 ppm H2. The SnO2-nanowire fabrication procedure based on spray pyrolysis and subsequent annealing is performed at atmospheric pressure, requires no vacuum and allows upscale of the substrate to a wafer size. 3D-integration with CMOS chips is proposed as viable way for practical realization of smart nanowire based gas sensor devices for the consumer market.

Direct absorption spectroscopy sensor for temperature and H2O concentration of flat flame burner

NASA Astrophysics Data System (ADS)

Duan, Jin-hu; Jin, Xing; Wang, Guang-yu; Qu, Dong-sheng

2016-01-01

A tunable diode laser absorption sensor, based on direct absorption spectroscopy and time division multiplexing scheme, was developed to measure H2O concentration and temperature of flat flame burner. At the height of 15mm from the furnace surface, temperature and concentration were measured at different equivalence ratios. Then the distance between the laser and the furnace surface was changed while the equivalence ratio was fixed at 1 and experiments were performed to measure temperature and H2O concentration at every height. At last flame temperatures and H2O concentrations were obtained by simulation and computational analysis and these combustion parameters were compared with the reference. The results showed that the experimental results were in accordance with the reference values. Temperature errors were less than 4% and H2O component concentration errors were less than 5%and both of them reached their maximum when the equivalent ratio was set at 1. The temperature and H2O concentration increased with the height from furnace surface to laser when it varied from 3mm to 9mm and it decreased when it varied from 9mm to 30mm and they reached their maximum at the height of 9mm. Keywords: tunable diode laser, direct absorption spectroscopy

The solubility of gold in H 2 O-H 2 S vapour at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2011-09-01

This experimental study sheds light on the complexation of gold in reduced sulphur-bearing vapour, specifically, in H 2O-H 2S gas mixtures. The solubility of gold was determined in experiments at temperatures of 300, 350 and 365 °C and reached 2.2, 6.6 and 6.3 μg/kg, respectively. The density of the vapour varied from 0.02 to 0.22 g/cm 3, the mole fraction of H 2S varied from 0.03 to 0.96, and the pressure in the cell reached 263 bar. Statistically significant correlations of the amount of gold dissolved in the fluid with the fugacity of H 2O and H 2S permit the experimental data to be fitted to a solvation/hydration model. According to this model, the solubility of gold in H 2O-H 2S gas mixtures is controlled by the formation of sulphide or bisulphide species solvated by H 2S or H 2O molecules. Formation of gold sulphide species is favoured statistically over gold bisulphide species and thus the gold is interpreted to dissolve according to reactions of the form: Au(s)+(n+1)HS(g)=AuS·(HS)n(g)+H(g) Au(s)+HS(g)+mHO(g)=AuS·(HO)m(g)+H(g) Equilibrium constants for Reaction (A1) and the corresponding solvation numbers ( K A1 and n) were evaluated from the study of Zezin et al. (2007). The equilibrium constants as well as the hydration numbers for Reaction (A2) ( K A2 and m) were adjusted simultaneously by a custom-designed optimization algorithm and were tested statistically. The resulting values of log K A2 and m are -15.3 and 2.3 at 300 and 350 °C and -15.1 and 2.2 at 365 °C, respectively. Using the calculated stoichiometry and stability of Reactions (A1) and (A2), it is now possible to quantitatively evaluate the contribution of reduced sulphur species to the transport of gold in aqueous vapour at temperatures up to 365 °C. This information will find application in modelling gold ore-forming processes in vapour-bearing magmatic hydrothermal systems, notably those of epithermal environments.

Strong Temperature Dependence in the Reactivity of H 2 on RuO 2 (110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.; Dahal, Arjun; Dohnálek, Zdenek

2016-08-04

The ability of hydrogen to facilitate many types of heterogeneous catalysis starts with its adsorption. As such, understanding the temperature-dependence sticking of H2 is critical toward controlling and optimizing catalytic conditions in those cases where adsorption is rate-limiting. In this work, we examine the temperature-dependent sticking of H2/D2 to the clean RuO2(110) surface using the King & Wells molecular beam approach, temperature programmed desorption (TPD) and scanning tunneling microscopy (STM). We show that the sticking probability (molecular or dissociative) of H2/D2 on this surface is highly temperature-dependent, decreasing from ~0.4-0.5 below 25 K to effectively zero above 200 K. Bothmore » STM and TPD reveal that OH/OD formation is severely limited for adsorption temperatures above ~150 K. Previous literature reports of extensive surface hydroxylation from H2/D2 exposures at room temperature were most likely the result of inadvertent contamination brought about from dosing by chamber backfilling.« less

Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

PubMed

Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

2017-11-22

Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

CKA2 functions in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NO accumulation in yeast.

PubMed

Liu, Wen-Cheng; Yuan, Hong-Mei; Li, Yun-Hui; Lu, Ying-Tang

2015-09-01

Nitric oxide (NO) plays key roles in yeast responses to various environmental factors, such as H2O2 and high temperature. However, the gene encoding NO synthase (NOS) in yeast has not yet been identified, and the mechanism underlying the regulation of NOS-like activity is poorly understood. Here, we report on the involvement of CKA2 in H2O2-induced yeast apoptosis and yeast high-temperature stress tolerance. Our results showed that although Δcka2 mutant had reduced NO accumulation with decreased apoptosis after H2O2 exposure, treatment with a NO donor, sodium nitroprusside, resulted in similar survival rate of Δcka2 mutant compared to that of wild-type yeast when subjected to H2O2 stress. This finding occurred because H2O2-enhanced NOS-like activity in wild-type yeast was significantly repressed in Δcka2. Our additional experiments indicated that both high-temperature-enhanced NO accumulation and NOS-like activity were also suppressed in Δcka2, leading to the hypersensitivity of the mutant to high temperature in terms of changes in survival rate. Thus, our results showed that CKA2 functioned in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NOS-like-dependent NO accumulation in yeast. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, Leo J.; Pratt, Harry; Staiger, Chad

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Temperature Dependence of the O + HO2 Rate Coefficient

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Wine, P. H.

1997-01-01

A pulsed laser photolysis technique has been employed to investigate the kinetics of the radical-radical reaction O((sup 3)P) + HO2 OH + O2 over the temperature range 266-391 K in 80 Torr of N2 diluent gas. O((sup 3)P) was produced by 248.5-nm KrF laser photolysis of O3 followed by rapid quenching of O(1D) to O((sup 3)P) while HO2 was produced by simultaneous photolysis of H2O2 to create OH radicals which, in turn, reacted with H2O2 to yield HO2. The O((sup 3)P) temporal profile was monitored by using time-resolved resonance fluorescence spectroscopy. The HO2 concentration was calculated based on experimentally measured parameters. The following Arrhenius expression describes our experimental results: k(sub 1)(T) equals (2.91 +/- 0.70) x 10(exp -11) exp[(228 +/- 75)/T] where the errors are 2 sigma and represent precision only. The absolute uncertainty in k, at any temperature within the range 266-391 K is estimated to be +/- 22 percent. Our results are in excellent agreement with a discharge flow study of the temperature dependence of k(sub 1) in 1 Torr of He diluent reported by Keyser, and significantly reduce the uncertainty in the rate of this important stratospheric reaction at subambient temperatures.

Influence of H2O on Liquidus Temperatures of Primitive Basalts and Olivine-Liquid Thermometry.

NASA Astrophysics Data System (ADS)

Medard, E.; Grove, T. L.

2005-12-01

We have undertaken a systematic experimental study aimed at understanding the effect of water on olivine liquidus temperatures of primitive basalts. Experiments have been performed on a primitive tholeiitic basalt from Medicine Lake Volcano, California (sample 82-72f, Bartels et al. 1991). The dry liquidus has been characterized from 0.1 MPa to 1.2 GPa. The wet liquidus has been constrained to within 15 °C using water-saturated experiments performed in a MHC externally heated pressure vessel. Preliminary results show that the olivine-liquidus depression (i.e., the difference between dry and water-bearing liquidus) is essentially a linear function of the water content of the melt: ΔT = 560  X(HO0.5), where X(HO0.5) is the mole fraction of water, calculated on a single-cation oxide basis. For 82-72f, this roughly translates into a 30 °C / wt% H2O depression. Simple systems (e.g., diopside/H2O, albite/H2O) suggest that melt structure / composition may have an influence on H2O liquidus depression, and this potential influence is currently under investigation. Experimental phase equilibria and thermobarometry of primitive basalts provide the primary evidence for estimating melting conditions and thermal structures in the Earth's mantle. Assessing the influence of H2O is critical, because it is the dominant volatile component involved in igneous processes, and it has been shown to cause a significant reduction in liquidus temperatures. However, recent model parameterizations vary from very large effects at low H2O contents (about 75 °C at 1 wt% H2O, Falloon and Danyushevsky 2000) to linear effect of H2O vs liquidus temperature (about 25 °C at 1 wt% H2O, Sugawara 2000). Our experimental determination more closely approximates the latter model. A key consequence is that the presence of small amounts of water in MORB magmas (< 1wt%) will only have a very small effect (< 30 °C) on liquidus temperature determination for mid-ocean-ridges. For magmas that are more

Ab initio molecular dynamics study of fluid H2O-CO2 mixture in broad pressure-temperature range

NASA Astrophysics Data System (ADS)

Fu, Jie; Zhao, Jijun; Plyasunov, Andrey V.; Belonoshko, Anatoly B.

2017-11-01

Properties of H2O and CO2 fluid and their mixtures under extreme pressures and temperatures are poorly known yet critically important in a number of applications. Several hundreds of first-principles molecular dynamics (FPMD) runs have been performed to obtain the pressure-volume-temperature (P-V-T) data on supercritical H2O, CO2, and H2O-CO2 mixtures. The pressure-temperature (P-T) range are from 0.5 GPa to 104 GPa (48.5 GPa for CO2) and from 600 K to 4000 K. Based on these data, we evaluate several existing equations of state (EOS) for the fluid H2O, CO2, and H2O-CO2 mixture. The results show that the EOS for H2O from Belonoshko et al. [Geochim. Cosmochim. Acta 55, 381-387; Geochim. Cosmochim. Acta 55, 3191-3208; Geochim. Cosmochim. Acta 56, 3611-3626; Comput. Geosci. 18, 1267-1269] not only can be used in the studied P-T range but also is accurate enough to be used for prediction of P-V-T data. In addition, IAPWS-95 EOS for H2O shows excellent extrapolation behavior beyond 1.0 GPa and 1273 K. However, for the case of CO2, none of the existing EOS produces data in agreement with the FPMD results. We created new EOS for CO2. The precision of the new EOS is tested by comparison to the calculated P-V-T data, fugacity coefficient of the CO2 fluid derived from high P-T experimental data as well as to the (very scarce) experimental volumetric data in the high P-T range. On the basis of our FPMD data we created a new EOS for H2O-CO2 mixture. The new EOS for the mixture is in reasonable agreement with experimental data.

The primary solar-type atmosphere surrounding the accreting Earth: H2O-induced high surface temperature.

NASA Astrophysics Data System (ADS)

Sasaki, S.

In the solar nebula, a growing planet attracts ambient gas to form a solar-type atmosphere. The structure of this H2-He atmosphere is calculated assuming the Earth was formed in the nebula. The blanketing effect of the atmosphere renders the planetary surface molten when the planetary mass exceeds 0.2 ME (ME being the present Earth's mass). Reduction of the surface melt by atmospheric H2 should add a large amount of H2O to the atmosphere: under the quartz-iron-fayalite oxygen buffer, partial pressure ratio P(H2O)/P(H2) becomes higher than 0.1. Enhancing opacity and gas mean molecular weight, the excess H2O raises the temperature and renders the atmosphere in convective equilibrium, while the dissociation of H2 suppresses the adiabatic temperature gradient. The surface temperature of the proto-Earth can be as high as 4700K when its mass is 1 ME. Such a high temperature may accelerate the evaporation of surface materials. A deep totally-molten magma ocean should exist in the accretion Earth.

Determining H2O Vapor Temperature and Concentration in Particle-Free and Particle-Laden Combustion Flows Using Spectral Line Emission Measurements

NASA Astrophysics Data System (ADS)

Tobiasson, John Robert

2017-07-01

There is a growing need for the clean generation of electricity in the world, and increased efficiency is one way to achieve cleaner generation. Increased efficiency may be achieved through an improved understanding of the heat flux of participating media in combustion environments. Real-time in-situ optical measurements of gas temperature and concentrations in combustion environments is needed. Optical methods do not disturb the flow characteristics and are not subject to the temperature limitation of current methods. Simpler, less-costly optical measurements than current methods would increase the ability to apply them in more circumstances. This work explores the ability to simultaneously measure gas temperature and H2O concentration via integrated spectral intensity ratios in regions where H2O is the dominant participating gas. This work considered combustion flows with and without fuel and soot particles, and is an extension of work previously performed by Ellis et al. [1]. Five different combustion regimes were used to investigate the robustness of the infrared intensity integral method first presented by Ellis et al. [1]. These included Post-Flame Natural Gas (PFNG), Post-Flame Medium Wood (PFMW), Post-Flame Fine Wood (PFFW), In-Flame Natural Gas (IFNG), and In-Flame Fine Wood (IFFW). Optical spectra were collected as a function of path length for each regime. Methods for processing the spectra to obtain gas temperature, gas concentration, broadband temperature, and broadband emissivity were developed. A one-dimensional spectral intensity model that allowed for specular reflection, and investigated differences between measured and modeled spectral intensities was created. It was concluded that excellent agreement (within 2.5%) was achieved between optical and suction pyrometer gas temperatures as long as 1) the optical probe and cold target used were well-aligned 2) the path length was greater than 0.3 m and 3) the intensity from broadband emitters within

Temperature-dependent field-effect carrier mobility in organic thin-film transistors with a gate SiO2 dielectric modified by H2O2 treatment

NASA Astrophysics Data System (ADS)

Lin, Yow-Jon; Hung, Cheng-Chun

2018-02-01

The effect of the modification of a gate SiO2 dielectric using an H2O2 solution on the temperature-dependent behavior of carrier transport for pentacene-based organic thin-film transistors (OTFTs) is studied. H2O2 treatment leads to the formation of Si(-OH) x (i.e., the formation of a hydroxylated layer) on the SiO2 surface that serves to reduce the SiO2 capacitance and weaken the pentacene-SiO2 interaction, thus increasing the field-effect carrier mobility ( µ) in OTFTs. The temperature-dependent behavior of carrier transport is dominated by the multiple trapping model. Note that H2O2 treatment leads to a reduction in the activation energy. The increased value of µ is also attributed to the weakening of the interactions of the charge carriers with the SiO2 dielectric that serves to reduce the activation energy.

Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp; Saito, Tatsuya; Matsumura, Daisuke

2015-06-07

The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups thanmore » the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the

Clofibric acid degradation in UV254/H2O2 process: effect of temperature.

PubMed

Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

2010-04-15

The degradation of clofibric acid (CA) in UV(254)/H(2)O(2) process under three temperature ranges, i.e. T1 (9.0-11.5 degrees C), T2 (19.0-21.0 degrees C) and T3 (29.0-30.0 degrees C) was investigated. The effects of solution constituents including NO(3)(-) and HCO(3)(-) anions, and humic acid (HA) on CA degradation were evaluated in Milli-Q waters. CA degradation behaviors were simulated with the pseudo-first-order kinetic model and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated. The results showed that higher temperature would favor CA degradation, and CA degradation was taken place mostly by indirect oxidation through the formation of OH radicals in UV(254)/H(2)O(2) process. In addition, the effects of both NO(3)(-) and HCO(3)(-) anions at two selected concentrations (1.0x10(-3) and 0.1 mol L(-1)) and HA (20 mg L(-1)) on CA degradation were investigated. The results showed that HA had negative effect on CA degradation, and this effect was much more apparent under low temperature condition. On the other hand, the inhibitive effect on CA degradation at both lower and higher concentrations of bicarbonate was observed, and this inhibitive effect was much more apparent at higher bicarbonate concentration and lower temperature condition. While, at higher nitrate concentration the inhibitive effect on CA degradation under three temperature ranges was observed, and with the temperature increase this negative effect was apparently weakened. However, at lower nitrate concentration a slightly positive effect on CA degradation was found under T2 and T3 conditions. Moreover, when using a real wastewater treatment plant (WWTP) effluent spiked with CA over 99% of CA removal could be achieved under 30 degrees C within only 15 min compared with 40 and 80 min under 20 and 10 degrees C respectively, suggesting a significant promotion in CA degradation under higher temperature condition. Therefore, it can be concluded that temperature plays an

LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

NASA Astrophysics Data System (ADS)

Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

2016-01-01

Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

PubMed

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

In situ H2O and temperature detection close to burning biomass pellets using calibration-free wavelength modulation spectroscopy

NASA Astrophysics Data System (ADS)

Qu, Zhechao; Schmidt, Florian M.

2015-04-01

The design and application of an H2O/temperature sensor based on scanned calibration-free wavelength modulation spectroscopy (CF-WMS) and a single tunable diode laser at 1.4 µm is presented. The sensor probes two H2O absorption peaks in a single scan and simultaneously retrieves H2O concentration and temperature by least-squares fitting simulated 1f-normalized 2f-WMS spectra to measured 2f/ 1f-WMS signals, with temperature, concentration and nonlinear modulation amplitude as fitting parameters. Given a minimum detectable absorbance of 1.7 × 10-5 cm-1 Hz-1/2, the system is applicable down to an H2O concentration of 0.1 % at 1,000 K and 20 cm path length (200 ppm·m). The temperature in a water-seeded laboratory-scale reactor (670-1220 K at 4 % H2O) was determined within an accuracy of 1 % by comparison with the reactor thermocouple. The CF-WMS sensor was applied to real time in situ measurements of H2O concentration and temperature time histories (0.25-s time resolution) in the hot gases 2-11 mm above biomass pellets during atmospheric combustion in the reactor. Temperatures between 1,200 and 1,600 K and H2O concentrations up to 40 % were detected above the biofuels.

Synthesis, structure, optical, photoluminescence and magnetic properties of K2[Co(C2O4)2(H2O)2]·4H2O

NASA Astrophysics Data System (ADS)

Narsimhulu, M.; Hussain, K. A.

2018-06-01

The synthesis, crystal structure, optical, photoluminescence and magnetic behaviour of potassium bis(oxalato)cobaltate(II)tertrahydrate{K2[Co(C2O4)2(H2O)2]·4H2O} are described. The compound was grown at room temperature from mixture of aqueous solutions by slow evaporation method. The X-ray crystallographic data showed that the compound belongs to the monoclinic crystal system with P21/n space group and Z = 4. The UV-visible diffuse absorbance spectra exhibited bands at 253, 285 and 541 nm in the visible and ultraviolet regions. The optical band gap of the compound was estimated as 3.4 eV. At room temperature, an intense photoluminescence was observed from this material around 392 nm when it excited at 254 nm. The variable temperature dc magnetic susceptibility measurements exposed paramagnetic behaviour at high temperatures and antiferromagnetic ordering at low temperatures.

Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

NASA Astrophysics Data System (ADS)

Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

2017-06-01

The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

Measurements of axisymmetric temperature and H2O concentration distributions on a circular flat flame burner based on tunable diode laser absorption tomography

NASA Astrophysics Data System (ADS)

Xia, Huihui; Kan, Ruifeng; Xu, Zhenyu; Liu, Jianguo; He, Yabai; Yang, Chenguang; Chen, Bing; Wei, Min; Yao, Lu; Zhang, Guangle

2016-10-01

In this paper, the reconstruction of axisymmetric temperature and H2O concentration distributions in a flat flame burner is realized by tunable diode laser absorption spectroscopy (TDLAS) and filtered back-projection (FBP) algorithm. Two H2O absorption transitions (7154.354/7154.353 cm-1 and 7467.769 cm-1) are selected as line pair for temperature measurement, and time division multiplexing technology is adopted to scan this two H2O absorption transitions simultaneously at 1 kHz repetition rate. In the experiment, FBP algorithm can be used for reconstructing axisymmetric distributions of flow field parameters with only single view parallel-beam TDLAS measurements, and the same data sets from the given parallel beam are used for other virtual projection angles and beams scattered between 0° and 180°. The real-time online measurements of projection data, i.e., integrated absorbance both for pre-selected transitions on CH4/air flat flame burner are realized by Voigt on-line fitting, and the fitting residuals are less than 0.2%. By analyzing the projection data from different views based on FBP algorithm, the distributions of temperature and concentration along radial direction can be known instantly. The results demonstrate that the system and the proposed innovative FBP algorithm are capable for accurate reconstruction of axisymmetric temperature and H2O concentration distribution in combustion systems and facilities.

Conductivity measurements on H 2O-bearing CO 2-rich fluids

DOE PAGES

Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

2014-09-10

Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H 2O to CO 2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO 2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H 2O concentrationsmore » up to ~1600 ppmw (xH 2O ≈ 3.9 x 10 -3), corresponding to the H 2O solubility limit in liquid CO 2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO 2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

Wavelength-modulation spectroscopy near 1.4 µm for measurements of H2O and temperature in high-pressure and -temperature gases

NASA Astrophysics Data System (ADS)

Goldenstein, C. S.; Spearrin, R. M.; Schultz, I. A.; Jeffries, J. B.; Hanson, R. K.

2014-05-01

The development, validation and demonstration of a two-color tunable diode laser (TDL) absorption sensor for measurements of temperature and H2O in high-pressure and high-temperature gases are presented. This sensor uses first-harmonic-normalized wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in harsh, high-pressure environments. Two telecommunications-grade TDLs were used to probe H2O absorption transitions near 1391.7 and 1469.3 nm. The lasers were frequency-multiplexed and modulated at 160 and 200 kHz to enable a measurement bandwidth up to 30 kHz along a single line-of-sight. In addition, accurate measurements are enabled at extreme conditions via an experimentally derived spectroscopic database. This sensor was validated under low-absorbance (<0.05) conditions in shock-heated H2O-N2 mixtures at temperatures and pressures from 700 to 2400 K and 2 to 25 atm. There, this sensor recovered the known temperature and H2O mole fraction with a nominal accuracy of 2.8% and 4.7% RMS, respectively. Lastly, this sensor resolved expected transients with high bandwidth and high precision in a reactive shock tube experiment and a pulse detonation combustor.

Post-deposition annealing temperature dependence TiO{sub 2}-based EGFET pH sensor sensitivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zulkefle, M. A., E-mail: alhadizulkefle@gmail.com; Rahman, R. A., E-mail: rohanieza.abdrahman@gmail.com; Yusoff, K. A., E-mail: khairul.aimi.yusof@gmail.com

EGFET pH sensor is one type of pH sensor that is used to measure and determine pH of a solution. The sensing membrane of EGFET pH sensor plays vital role in the overall performance of the sensor. This paper studies the effects of different annealing temperature of the TiO{sub 2} sensing membranes towards sensitivity of EGFET pH sensor. Sol-gel spin coating was chosen as TiO{sub 2} deposition techniques since it is cost-effective and produces thin film with uniform thickness. Deposited TiO{sub 2} thin films were then annealed at different annealing temperatures and then were connected to the gate of MOSFETmore » as a part of the EGFET pH sensor structure. The thin films now act as sensing membranes of the EGFET pH sensor and sensitivity of each sensing membrane towards pH was measured. From the results it was determined that sensing membrane annealed at 300 °C gave the highest sensitivity followed by sample annealed at 400 °C and 500 °C.« less

The TAED/H2O2/NaHCO3 system as an approach to low-temperature and near-neutral pH bleaching of cotton.

PubMed

Long, Xiaoxia; Xu, Changhai; Du, Jinmei; Fu, Shaohai

2013-06-05

A low-temperature and near-neutral pH bleaching system was conceived for cotton by incorporating TAED, H2O2 and NaHCO3. The TAED/H2O2/NaHCO3 system was investigated and optimized for bleaching of cotton using a central composite design (CCD) combined with response surface methodology (RSM). CCD experimental data were fitted to create a response surface quadratic model (RSQM) describing the degree of whiteness of bleached cotton fabric. Analysis of variance for the RSQM revealed that temperature was the most significant variable, followed by [TAED] and time, while [NaHCO3] was insignificant. An effective system was conducted by adding 5.75 g L(-1) TAED together with H2O2 and NaHCO3 at a molar ratio of 1:2.4:2.8 and applied to bleaching of cotton at 70 °C for 40 min. Compared to a commercial bleaching method, the TAED/H2O2/NaHCO3 system provided cotton with comparable degree of whiteness, slightly inferior water absorbency and acceptable dyeability, but had competitive advantage in protecting cotton from severe chemical damage in bleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeniyi Lawal

We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant tomore » produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the

Quantitative Measurements of HO2 and other products of n-butane oxidation (H2O2, H2O, CH2O, and C2H4) at elevated temperatures by direct coupling of a jet-stirred reactor with sampling nozzle and cavity ring-down spectroscopy (cw-CRDS).

PubMed

Djehiche, Mokhtar; Le Tan, Ngoc Linh; Jain, Chaithanya D; Dayma, Guillaume; Dagaut, Philippe; Chauveau, Christian; Pillier, Laure; Tomas, Alexandre

2014-11-26

For the first time quantitative measurements of the hydroperoxyl radical (HO2) in a jet-stirred reactor were performed thanks to a new experimental setup involving fast sampling and near-infrared cavity ring-down spectroscopy at low pressure. The experiments were performed at atmospheric pressure and over a range of temperatures (550-900 K) with n-butane, the simplest hydrocarbon fuel exhibiting cool flame oxidation chemistry which represents a key process for the auto-ignition in internal combustion engines. The same technique was also used to measure H2O2, H2O, CH2O, and C2H4 under the same conditions. This new setup brings new scientific horizons for characterizing complex reactive systems at elevated temperatures. Measuring HO2 formation from hydrocarbon oxidation is extremely important in determining the propensity of a fuel to follow chain-termination pathways from R + O2 compared to chain branching (leading to OH), helping to constrain and better validate detailed chemical kinetics models.

Room-temperature H2S Gas Sensor Based on Au-doped ZnFe2O4 Yolk-shell Microspheres.

PubMed

Yan, Yin; Nizamidin, Patima; Turdi, Gulmira; Kari, Nuerguli; Yimit, Abliz

2017-01-01

Room-temperature type H 2 S sensing devices that use Au-doped ZnFe 2 O 4 yolk-shell microspheres as the active material have been fabricated using a solvothermal method as well as subsequent annealing and a chemical etching process. The samples are characterized using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). The results demonstrate that the doping of Au does not change the spinel structure of the products, which were yolk-shell microspheres, while the particle size varied with the Au doping concentration. Also, the as-fabricated sensor device exhibited excellent selectivity toward H 2 S gas at the room temperature; the gas-sensing property of 2 wt% Au-doped ZnFe 2 O 4 microspheres was the best. The Au-doped ZnFe 2 O 4 yolk-shell microspheres can be promising as a sensing material for H 2 S gas detecting at room temperature.

High-bandwidth scanned-wavelength-modulation spectroscopy sensors for temperature and H2O in a rotating detonation engine

NASA Astrophysics Data System (ADS)

Goldenstein, Christopher S.; Almodóvar, Christopher A.; Jeffries, Jay B.; Hanson, Ronald K.; Brophy, Christopher M.

2014-10-01

The design and use of two-color tunable diode laser (TDL) absorption sensors for measurements of temperature and H2O in a rotating detonation engine (RDE) are presented. Both sensors used first-harmonic-normalized scanned-wavelength-modulation spectroscopy with second-harmonic detection (scanned-WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in the harsh combustion environment. One sensor used two near-infrared (NIR) TDLs near 1391.7 nm and 1469.3 nm that were modulated at 225 kHz and 285 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O absorption transitions to provide a measurement rate of 50 kHz and a detection limit in the RDE of 0.2% H2O by mole. The other sensor used two mid-infrared (MIR) TDLs near 2551 nm and 2482 nm that were modulated at 90 kHz and 112 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O transitions to provide a measurement rate of 10 kHz and a detection limit in the RDE of 0.02% H2O by mole. Four H2O absorption transitions with different lower-state energies were used to assess the homogeneity of temperature in the measurement plane. Experimentally derived spectroscopic parameters that enable temperature and H2O sensing to within 1.5-3.5% of known values are reported. The sensor design enabling the high-bandwidth scanned-WMS-2f/1f measurements is presented. The two sensors were deployed across two orthogonal and coplanar lines-of-sight (LOS) located in the throat of a converging-diverging nozzle at the RDE combustor exit. Measurements in the non-premixed H2-fueled RDE indicate that the temperature and H2O oscillate at the detonation frequency (≈3.25 kHz) and that production of H2O is a weak function of global equivalence ratio.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

Vibrational energy transfer and relaxation in O2 and H2O.

PubMed

Huestis, David L

2006-06-01

Near-resonant vibrational energy exchange between oxygen and water molecules is an important process in the Earth's atmosphere, combustion chemistry, and the chemical oxygen iodine laser (COIL). The reactions in question are (1) O2(1) + O2(0) --> O2(0) + O2(0); (2) O2(1) + H2O(000) --> O2(0) + H2O(000); (3) O2(1) + H2O(000) <--> O2(0) + H2O(010); (4) H2O(010) + H2O(000) --> H2O(000) + H2O(000); and (5) H2O(010) + O2(0) --> H2O(000) + O2(0). Reanalysis of the data available in the chemical kinetics literature provides reliable values for rate coefficients for reactions 1 and 4 and strong evidence that reactions 2 and 5 are slow in comparison with reaction 3. Analytical solution of the chemical rate equations shows that previous attempts to measure the rate of reaction 3 are unreliable unless the water mole fraction is higher than 1%. Reanalysis of data from the only experiment satisfying this constraint provides a rate coefficient of (5.5 +/- 0.4) x 10(-13) cm3/s at room temperature, between the values favored by the atmospheric and laser modeling communities.

Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

NASA Technical Reports Server (NTRS)

Carter, H. G.; Bullock, R. E.

1972-01-01

Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions.

PubMed

Zhang, R H; Zhang, X T; Hu, S M

2008-04-15

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.

Tracking the energy flow in the hydrogen exchange reaction OH + H2O → H2O + OH.

PubMed

Zhu, Yongfa; Ping, Leilei; Bai, Mengna; Liu, Yang; Song, Hongwei; Li, Jun; Yang, Minghui

2018-05-09

The prototypical hydrogen exchange reaction OH + H2O → H2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on ∼44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.

Insights into the distribution of water in a self-humidifying H2/O2 proton-exchange membrane fuel cell using 1H NMR microscopy.

PubMed

Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

2006-11-01

Proton ((1)H) NMR microscopy is used to investigate in-situ the distribution of water throughout a self-humidifying proton-exchange membrane fuel cell, PEMFC, operating at ambient temperature and pressure on dry H(2)(g) and O(2)(g). The results provide the first experimental images of the in-plane distribution of water within the PEM of a membrane electrode assembly in an operating fuel cell. The effect of gas flow configuration on the distribution of water in the PEM and cathode flow field is investigated, revealing that the counter-flow configurations yield a more uniform distribution of water throughout the PEM. The maximum power output from the PEMFC, while operating under conditions of constant external load, occurs when H(2)O(l) is first visible in the (1)H NMR image of the cathode flow field, and subsequently declines as this H(2)O(l) continues to accumulate. The (1)H NMR microscopy experiments are in qualitative agreement with predictions from several theoretical modeling studies (e.g., Pasaogullari, U.; Wang, C. Y. J. Electrochem. Soc. 2005, 152, A380-A390), suggesting that combined theoretical and experimental approaches will constitute a powerful tool for PEMFC design, diagnosis, and optimization.

Enhanced H2 sensitivity at room temperature of ZnO nanowires functionalized by Pd nanoparticles

NASA Astrophysics Data System (ADS)

Ren, Shoutian; Fan, Guanghua; Qu, Shiliang; Wang, Qiang

2011-10-01

For sensitive detection of H2, ZnO nanowires networks decorated with photo-decomposed Pd nanoparticles were fabricated between femtosecond laser-writing interdigitated electrodes by chemical vapor deposition method. When H2 concentration is increased from 20 to 4000 ppm at room temperature, sensitivity of the sample is increased from 3.7% to 1017.9%. The high sensitivity can be explained by considering the reaction between the adsorbed O2- and the disassociated H atoms facilitated by Pd nanoparticles. This mechanism is further supported by the H2 response results under UV light illumination, which can reduce the amount of O2- on the ZnO surface, leading to depressed sensitivity. The sensor also shows high selectivity, long-term stability, and ultra-low power consumption of nanowatt level, due to the novel fabrication process.

Diagnostic system for measuring temperature, pressure, CO2 concentration and H2O concentration in a fluid stream

DOE Office of Scientific and Technical Information (OSTI.GOV)

Partridge, Jr., William P.; Jatana, Gurneesh Singh; Yoo, Ji-Hyung

A diagnostic system for measuring temperature, pressure, CO.sub.2 concentration and H.sub.2O concentration in a fluid stream is described. The system may include one or more probes that sample the fluid stream spatially, temporally and over ranges of pressure and temperature. Laser light sources are directed down pitch optical cables, through a lens and to a mirror, where the light sources are reflected back, through the lens to catch optical cables. The light travels through the catch optical cables to detectors, which provide electrical signals to a processer. The processer utilizes the signals to calculate CO.sub.2 concentration based on the temperaturesmore » derived from H.sub.2O vapor concentration. A probe for sampling CO.sub.2 and H.sub.2O vapor concentrations is also disclosed. Various mechanical features interact together to ensure the pitch and catch optical cables are properly aligned with the lens during assembly and use.« less

In situ combustion measurements of H2O and temperature near 2.5 µm using tunable diode laser absorption

NASA Astrophysics Data System (ADS)

Farooq, Aamir; Jeffries, Jay B.; Hanson, Ronald K.

2008-07-01

In situ combustion measurements of water vapor concentration and gas temperature were carried out with a new tunable diode laser sensor near 2.5 µm. Recent availability of room-temperature semiconductor diode lasers operating at longer wavelengths provides access to fundamental vibrational bands (ν1 and ν3) of H2O. These bands have stronger absorption line strength compared to the overtone (2ν1, 2ν3) and combination (ν1 + ν3) vibrational bands in the near-infrared region probed previously with telecommunication diode lasers. The absorption transitions of H2O vapor in the 2.5-3.0 µm region are systematically analyzed via spectral simulation, and optimal spectral line pairs are selected for combustion measurements in the temperature range of 1000-2500 K. Fundamental spectroscopic parameters (line strength, line position and line-broadening coefficients) of the selected transitions are determined via laboratory measurements in a heated cell. Absorption measurements of H2O concentration and temperature are then made in a laboratory flat-flame burner to illustrate the potential of this sensor for sensitive and accurate measurements in combustion gases with short optical path lengths.

Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

2014-07-17

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Chen, Long

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« less

Transfer of a proton between H2 and O2.

PubMed

Kluge, Lars; Gärtner, Sabrina; Brünken, Sandra; Asvany, Oskar; Gerlich, Dieter; Schlemmer, Stephan

2012-11-13

The proton affinities of hydrogen and oxygen are very similar. Therefore, it has been discussed that the proton transfer from the omnipresent H(3)(+) to molecular oxygen in the near thermoneutral reaction H(3)(+) + O(2) <--> O(2)H(+) + H(2) effectively binds the interstellar oxygen in O(2)H(+). In this work, the proton transfer reaction has been investigated in a low-temperature 22-pole ion trap from almost room temperature (280 K) down to the lowest possible temperature limited by freeze out of oxygen gas (about 40 K at a low pressure). The Arrhenius behaviour of the rate coefficient for the forward reaction shows that it is subject to an activation energy of E(A)/k=113 K. Thus, the forward reaction can proceed only in higher temperature molecular clouds. Applying laser-induced reactions to the given reaction (in the backward direction), a preliminary search for spectroscopic signatures of O(2)H(+) in the infrared was unsuccessful, whereas the forward reaction has been successfully used to probe the population of the lowest ortho and para levels of H(3)(+).

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2011-03-01

"H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

NASA Astrophysics Data System (ADS)

Johannes, Wilhelm

1980-09-01

Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this

Measurements and Modeling of SiCl(4) Combustion in a Low-Pressure H2/O2 Flame

DTIC Science & Technology

2006-11-10

temperature and OH concentration profiles as a function of distance from a McKenna-style burner in premixed, one-dimensional, low-pressure H2/0 2/Ar SiCl4 ...profiles for hydrogen/oxygen flames with and without SiCl4 ....... . .. . .. . . . . . 15 111,o Tables 1. Silicon Tetrachloride Proposed Combustion...studied with and without SiCI4 precursor at concentrations of 0.5% of the H 2 + 02 flow. For the experiments doped with SiCl4 , the oxygen flow exiting the

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

NASA Technical Reports Server (NTRS)

Isham, M. A.

1992-01-01

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

VUV photoionization cross sections of HO2, H2O2, and H2CO.

PubMed

Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

2015-02-26

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

Effect of mild-temperature H2O2 oxidation on solubilization and anaerobic digestion of waste activated sludge.

PubMed

Junga, Heejung; Kim, Jaai; Lee, Seungyong; Lee, Changsoo

2014-08-01

Efficient sludge management is among the most challenging issues in wastewater treatment today, and anaerobic digestion is regarded as a viable solution. Mild-temperature H202 oxidation was examined for enhanced solubilization and biogas production of waste activated sludge (WAS). The effects of pretreatment factors (i.e. temperature and H202 concentration) on the degree of WAS disintegration (DD) and biogas yield (BY) were assessed by response surface analysis within the design space of 60-90 degrees C and 0-200mM H202. Significant sludge disintegration (up to 23.0% DD) and visibly enhanced BY (up to 26.9%) were shown in the pretreatment trials. Two response surface models to describe how DD and BY respond to changes in the pretreatment conditions were successfully constructed (R2 > 0.95, p < 0.05). The models showed totally different response surface shapes, indicating the DD and BY were influenced by pretreatment conditions in very different ways. DD was dominantly affected by temperature and showed higher model responses at the high-temperature region, while the BY response peaked in the low-temperature and mid-level H2O2 region. This observation implies that the enhanced solubilization of WAS was not directly translated into an increase in biogas production. Our results showed that WAS can be efficiently disintegrated by H202 oxidation under mild-temperature conditions for enhanced anaerobic digestibility. Within the explored region of pretreatment conditions, the maximum BY was estimated to be 82.1 mL/gCODadded (32.8% greater than the untreated control) at (60.0 degrees C, 74.2 mM H2O2).

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

NASA Astrophysics Data System (ADS)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

NASA Astrophysics Data System (ADS)

Santamaria, M.; Pecoraro, C. M.; Di Quarto, F.; Bocchetta, P.

2015-02-01

Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H2-O2 fuel cell allowing to get peak power densities up to 350 mW cm-2. Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm-1.

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

Stepwise formation of H3O(+)(H2O)n in an ion drift tube: Empirical effective temperature of association/dissociation reaction equilibrium in an electric field.

PubMed

Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M

2016-06-14

We measured equilibrium constants for H3O(+)(H2O)n-1 + H2O↔H3O(+)(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔHn,n-1 (0) and ΔSn,n-1 (0), of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O(+)(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.

Temperature and H2O sensing in laminar premixed flames using mid-infrared heterodyne phase-sensitive dispersion spectroscopy

NASA Astrophysics Data System (ADS)

Ma, Liuhao; Wang, Zhen; Cheong, Kin-Pang; Ning, Hongbo; Ren, Wei

2018-06-01

We report the first demonstration of heterodyne phase-sensitive dispersion spectroscopy (HPSDS) for the simultaneous temperature and H2O concentration measurements in combustion environments. Two continuous-wave distributed-feedback quantum cascade lasers (DFB-QCLs) at 5.27 and 10.53 µm were used to exploit the strong H2O transitions (1897.52 and 949.53 cm-1) at high temperatures. The injection current of each QCL was modulated at sub-GHz or GHz to generate the three-tone radiation and the dispersion signal was detected by the radio-frequency down-conversion heterodyning. The peak-to-peak ratio of the two H2O dispersion spectra exhibits a monotonic relationship with temperature over the temperature range of 1000-3000 K, indicating the capability of performing two-line thermometry using laser dispersion spectroscopy. We measured the temperatures of CH4/air flames at different equivalence ratios ( Φ = 0.8-1.2), yielding a good agreement with the corresponding thermocouple measurements. In addition, one-dimensional kinetic modeling coupled with a detailed chemical kinetic mechanism (GRI 3.0) was conducted to compare with the measured H2O concentrations using HPSDS. Finally, we demonstrated HPSDS is immune to optical power fluctuations by measuring the dispersion spectra at varied incident laser powers.

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

DOE PAGES

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

2016-04-16

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

Direct N2H4/H2O2 Fuel Cells Powered by Nanoporous Gold Leaves

PubMed Central

Yan, Xiuling; Meng, Fanhui; Xie, Yun; Liu, Jianguo; Ding, Yi

2012-01-01

Dealloyed nanoporous gold leaves (NPGLs) are found to exhibit high electrocatalytic properties toward both hydrazine (N2H4) oxidation and hydrogen peroxide (H2O2) reduction. This observation allows the implementation of a direct hydrazine-hydrogen peroxide fuel cell (DHHPFC) based on these novel porous membrane catalysts. The effects of fuel and oxidizer flow rate, concentration and cell temperature on the performance of DHHPFC are systematically investigated. With a loading of ~0.1 mg cm−2 Au on each side, an open circuit voltage (OCV) of 1.2 V is obtained at 80°C with a maximum power density 195 mW cm−2, which is 22 times higher than that of commercial Pt/C electrocatalyst at the same noble metal loading. NPGLs thus hold great potential as effective and stable electrocatalysts for DHHPFCs. PMID:23230507

H2O2 mediates ALA-induced glutathione and ascorbate accumulation in the perception and resistance to oxidative stress in Solanum lycopersicum at low temperatures.

PubMed

Liu, Tao; Hu, Xiaohui; Zhang, Jiao; Zhang, Junheng; Du, Qingjie; Li, Jianming

2018-02-15

Low temperature is a crucial factor influencing plant growth and development. The chlorophyll precursor, 5-aminolevulinic acid (ALA) is widely used to improve plant cold tolerance. However, the interaction between H 2 O 2 and cellular redox signaling involved in ALA-induced resistance to low temperature stress in plants remains largely unknown. Here, the roles of ALA in perceiving and regulating low temperature-induced oxidative stress in tomato plants, together with the roles of H 2 O 2 and cellular redox states, were characterized. Low concentrations (10-25 mg·L - 1 ) of ALA enhanced low temperature-induced oxidative stress tolerance of tomato seedlings. The most effective concentration was 25 mg·L - 1 , which markedly increased the ratio of reduced glutathione and ascorbate (GSH and AsA), and enhanced the activities of superoxide dismutase, catalase, ascorbate peroxidase, dehydroascorbate reductase, and glutathione reductase. Furthermore, gene expression of respiratory burst oxidase homolog1 and H 2 O 2 content were upregulated with ALA treatment under normal conditions. Treatment with exogenous H 2 O 2 , GSH, and AsA also induced plant tolerance to oxidative stress at low temperatures, while inhibition of GSH and AsA syntheses significantly decreased H 2 O 2 -induced oxidative stress tolerance. Meanwhile, scavenging or inhibition of H 2 O 2 production weakened, but did not eliminate, GSH- or AsA- induced tomato plant tolerance to oxidative stress at low temperatures. Appropriate concentrations of ALA alleviated the low temperature-induced oxidative stress in tomato plants via an antioxidant system. The most effective concentration was 25 mg·L - 1 . The results showed that H 2 O 2 induced by exogenous ALA under normal conditions is crucial and may be the initial step for perception and signaling transmission, which then improves the ratio of GSH and AsA. GSH and AsA may then interact with H 2 O 2 signaling, resulting in enhanced antioxidant capacity

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Noninvasive parametric blood flow imaging of head and neck tumours using [15O]H2O and PET/CT.

PubMed

Komar, Gaber; Oikonen, Vesa; Sipilä, Hannu; Seppänen, Marko; Minn, Heikki

2012-11-01

The aim of this study was to develop a simple noninvasive method for measuring blood flow using [15O]H2O PET/CT for the head and neck area applicable in daily clinical practice. Fifteen dynamic [15O]H2O PET emission scans with simultaneous online radioactivity measurements of radial arterial blood [Blood-input functions (IFs)] were performed. Two noninvasively obtained population-based input functions were calculated by averaging all Blood-IF curves corrected for patients' body mass and injected dose [standardized uptake value (SUV)-IF] and for body surface area (BSA-IF) and injected dose. Parametric perfusion images were calculated for each set of IFs using a linearized two-compartment model, and values for several tissues were compared using Blood-IF as the gold standard. On comparing all tissues, the correlation between blood flow obtained with the invasive Blood-IF and both SUV-IF and BSA-IF was significant (R2=0.785 with P<0.001 and R2=0.813 with P<0.001, respectively). In individual tissues, the performance of the two noninvasive methods was most reliable in resting muscle and slightly less reliable in tumour and cerebellar regions. In these two tissues, only BSA-IF showed a significant correlation with Blood-IF (R2=0.307 with P=0.032 in tumours and R2=0.398 with P<0.007 in the cerebellum). The BSA-based noninvasive method enables clinically relevant delineation between areas of low and high blood flow in tumours. The blood flow of low-perfusion tissues can be reliably quantified using either of the evaluated noninvasive methods.

Nafion-coating of the electrodes improves the flow-stability of the Ag/SiO2/Ag2O electroosmotic pump.

PubMed

Shin, Woonsup; Zhu, Enhua; Nagarale, Rajaram Krishna; Kim, Chang Hwan; Lee, Jong Myung; Shin, Samuel Jaeho; Heller, Adam

2011-06-15

When a current or a voltage is applied across the ceramic membrane of the nongassing Ag/Ag(2)O-SiO(2)-Ag/Ag(2)O pump, protons produced in the anodic reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-) are driven to the cathode, where they are consumed by the reaction Ag(2)O(s) + H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). The flow of water is induced by momentum transfer from the electric field-driven proton-sheet at the surface of the ceramic membrane. About 10(4) water molecules flowed per reacted electron. Because dissolved ions decrease the field at the membrane surface, the flow decreases upon increasing the ionic strength. For this reason Ag(+) ions introduced through the anodic reaction and by dissolution of Ag(2)O decrease the flow. Their accumulation is reduced by applying Nafion-films to the electrodes. The 20 μL min(-1) flow rate of 6 mm i.d. pumps with Nafion coated electrodes operate daily for 5 min at 1 V for 1 month, for 70 h when the pump is pulsed for 30 s every 30 min, and for 2 h when operating continuously.

Improvement in surface hydrophilicity and resistance to deformation of natural leather through O2/H2O low-temperature plasma treatment

NASA Astrophysics Data System (ADS)

You, Xuewei; Gou, Li; Tong, Xingye

2016-01-01

The natural leather was modified through O2/H2O low-temperature plasma treatment. Surface morphology was characterized by scanning electron microscopy (SEM) and the results showed that the pores on the leather surface became deeper and larger with enhanced permeability of water and vapor. XPS and FTIR-ATR was performed to determine the chemical composition of natural leather surface. Oxygen-containing groups were successfully grafted onto the surface of natural leather and oxygen content increased with longer treatment time. After O2/H2O plasma treatment, initial water contact angle was about 21° and water contact angles were not beyond 55° after being stored for 3 days. Furthermore, the tensile test indicated that the resistance to deformation had a prominent transform without sacrificing the tensile strength.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

Temperature and pressure dependent thermodynamic behavior of 2H-CuInO2

NASA Astrophysics Data System (ADS)

Bhamu, K. C.

2018-05-01

Density functional theory and quasi-harmonic Debye model has been used to study the thermodynamic properties of 2H-CuInO2. At the optimized structural parameters, pressure (0 to 80 GPa) dependent variation in the various thermodynamic properties, i.e. unit cell volume (V), bulk modulus (B), specific heat (Cv), Debye temperature (θD), Grüneisen parameter (γ) and thermal expansion coefficient (α) are calculated for various temperature values. The results predict that the pressure has significant effect on unit cell volume and bulk modulus while the temperature shows negligible effect on both parameters. With increasing temperature thermal expansion coefficient increase while with increasing pressure it decreases. The specific heat remains close to zero for ambient pressure and temperature values and it increases with increasing temperature. It is observed that the pressure has high impact on Debye temperature and Grüneisen parameter instead of temperature. Debye temperature and Grüneisen parameter both remains almost constant for the temperature range (0-300K) while Grüneisen parameter decrease with increasing pressure at constant temperature and Debye temperature increases rapidly with increasing pressure. An increase in Debye temperature with respect to pressure shows that the thermal vibration frequency changes rapidly.

Simultaneous measurement of 2-dimensional H2O concentration and temperature distribution in premixed methane/air flame using TDLAS-based tomography technology

NASA Astrophysics Data System (ADS)

Wang, Fei; Wu, Qi; Huang, Qunxing; Zhang, Haidan; Yan, Jianhua; Cen, Kefa

2015-07-01

An innovative tomographic method using tunable diode laser absorption spectroscopy (TDLAS) and algebraic reconstruction technique (ART) is presented in this paper for detecting two-dimensional distribution of H2O concentration and temperature in a premixed flame. The collimated laser beam emitted from a low cost diode laser module was delicately split into 24 sub-beams passing through the flame from different angles and the acquired laser absorption signals were used to retrieve flame temperature and H2O concentration simultaneously. The efficiency of the proposed reconstruction system and the effect of measurement noise were numerically evaluated. The temperature and H2O concentration in flat methane/air premixed flames under three different equivalence ratios were experimentally measured and reconstruction results were compared with model calculations. Numerical assessments indicate that the TDLAS tomographic system is capable for temperature and H2O concentration profiles detecting even the noise strength reaches 3% of absorption signal. Experimental results under different combustion conditions are well demonstrated along the vertical direction and the distribution profiles are in good agreement with model calculation. The proposed method exhibits great potential for 2-D or 3-D combustion diagnostics including non-uniform flames.

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Lyons, M.; Siegel, E.

2010-03-01

``Water water everywhere; ne'er a drop to drink''[Coleridg(1798)]; now:``Hydrogen hydrogen everywhere;STILL ne'er a drop to drink'': ONLY H2 can be ``FLYING-WATER''/``chemical-rain-in-pipelines''/ ``Hindenberg-effect (H2-UP;H2O-DOWN): atomic-weights ratio: O/H2O=[16]/[18]˜90%; O already in air uphill; NO H2O pumping need! In water-starved glacial-melting world, rescue ONLY by Siegel[3rd Intl.Conf.Alt.Energy,Hemisphere/Springer(1980)- vol.5/ p.459]Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating- system. Rosenfeld[Sci.315,1396(3/9/2007)]-Biello[Sci.Am.(3/9/ 2007)]crucial geomorphology which ONLY maximal-buoyancy light- est-element H2 can exploit, to again make ``Mountains into Fount- ains": Siegel ``terra-forming''(and ocean-rebasificaton!!!) long pre-``Holdren''-``Ciccerine" ``geo-enginering'', only via Siegel proprietary magnetic-hydrogen-valve permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Sci.300,1740(03)]global-pandemics (cancers/blindness/famine)dire-warning about H2-(ALONE)economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!

Fabrication of porous silicon nanowires by MACE method in HF/H2O2/AgNO3 system at room temperature

PubMed Central

2014-01-01

In this paper, the moderately and lightly doped porous silicon nanowires (PSiNWs) were fabricated by the ‘one-pot procedure’ metal-assisted chemical etching (MACE) method in the HF/H2O2/AgNO3 system at room temperature. The effects of H2O2 concentration on the nanostructure of silicon nanowires (SiNWs) were investigated. The experimental results indicate that porous structure can be introduced by the addition of H2O2 and the pore structure could be controlled by adjusting the concentration of H2O2. The H2O2 species replaces Ag+ as the oxidant and the Ag nanoparticles work as catalyst during the etching. And the concentration of H2O2 influences the nucleation and motility of Ag particles, which leads to formation of different porous structure within the nanowires. A mechanism based on the lateral etching which is catalyzed by Ag particles under the motivation by H2O2 reduction is proposed to explain the PSiNWs formation. PMID:24910568

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2013-03-01

''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

Calculation of the rate constant for state-selected recombination of H+O2(v) as a function of temperature and pressure

NASA Astrophysics Data System (ADS)

Teitelbaum, Heshel; Caridade, Pedro J. S. B.; Varandas, António J. C.

2004-06-01

Classical trajectory calculations using the MERCURY/VENUS code have been carried out on the H+O2 reactive system using the DMBE-IV potential energy surface. The vibrational quantum number and the temperature were selected over the ranges v=0 to 15, and T=300 to 10 000 K, respectively. All other variables were averaged. Rate constants were determined for the energy transfer process, H+O2(v)-->H+O2(v''), for the bimolecular exchange process, H+O2(v)-->OH(v')+O, and for the dissociative process, H+O2(v)-->H+O+O. The dissociative process appears to be a mere extension of the process of transferring large amounts of energy. State-to-state rate constants are given for the exchange reaction, and they are in reasonable agreement with previous results, while the energy transfer and dissociative rate constants have never been reported previously. The lifetime distributions of the HO2 complex, calculated as a function of v and temperature, were used as a basis for determining the relative contributions of various vibrational states of O2 to the thermal rate coefficients for recombination at various pressures. This novel approach, based on the complex's ability to survive until it collides in a secondary process with an inert gas, is used here for the first time. Complete falloff curves for the recombination of H+O2 are also calculated over a wide range of temperatures and pressures. The combination of the two separate studies results in pressure- and temperature-dependent rate constants for H+O2(v)(+Ar)⇄HO2(+Ar). It is found that, unlike the exchange reaction, vibrational and rotational-translational energy are liabilities in promoting recombination.

Diagnostic system for measuring temperature, pressure, CO.sub.2 concentration and H.sub.2O concentration in a fluid stream

DOE Office of Scientific and Technical Information (OSTI.GOV)

Partridge, Jr., William P.; Jatana, Gurneesh Singh; Yoo, Ji Hyung

A diagnostic system for measuring temperature, pressure, CO.sub.2 concentration and H.sub.2O concentration in a fluid stream is described. The system may include one or more probes that sample the fluid stream spatially, temporally and over ranges of pressure and temperature. Laser light sources are directed down pitch optical cables, through a lens and to a mirror, where the light sources are reflected back, through the lens to catch optical cables. The light travels through the catch optical cables to detectors, which provide electrical signals to a processer. The processer utilizes the signals to calculate CO.sub.2 concentration based on the temperaturesmore » derived from H.sub.2O vapor concentration. A probe for sampling CO.sub.2 and H.sub.2O vapor concentrations is also disclosed. Various mechanical features interact together to ensure the pitch and catch optical cables are properly aligned with the lens during assembly and use.« less

Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

NASA Astrophysics Data System (ADS)

Marion, Giles M.

2001-06-01

Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

The effect of H2O and CO2 on planetary mantles

NASA Technical Reports Server (NTRS)

Wyllie, P. J.

1978-01-01

The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

O and temperature in a hydrocarbon-fueled scramjet combustor

NASA Astrophysics Data System (ADS)

Goldenstein, C. S.; Schultz, I. A.; Spearrin, R. M.; Jeffries, J. B.; Hanson, R. K.

2014-09-01

The design and demonstration of a two-color tunable diode laser sensor for measurements of temperature and H2O in an ethylene-fueled model scramjet combustor are presented. This sensor probes multiple H2O transitions in the fundamental vibration bands near 2.5 μm that are up to 20 times stronger than those used by previous near-infrared H2O sensors. In addition, two design measures enabled high-fidelity measurements in the nonuniform flow field. (1) A recently developed calibration-free scanned-wavelength-modulation spectroscopy spectral-fitting strategy was used to infer the integrated absorbance of each transition without a priori knowledge of the absorption lineshape and (2) transitions with strengths that scale near-linearly with temperature were used to accurately determine the H2O column density and the H2O-weighted path-averaged temperature from the integrated absorbance of two transitions.

Solubilities of inert gases and methane in H2O and in D2O in the temperature range of 300 to 600 K

NASA Astrophysics Data System (ADS)

Crovetto, Rosa; Fernández-Prini, R.; Japas, María Laura

1982-01-01

The solubility of inert gases and methane in H2O and D2O has been measured between room temperature and 600 K. The calculation of Henry's constants kH, from the solubility data is analyzed in detail; if due account is taken of the nonideality in the gas phase, they can be determined unambiguously up to 520 K. Above this temperature, the ambiguity in kH increases sharply as contributions of third and higher order virial coefficients to the equation of state of the gaseous mixture become more important. The differences of gas solubilities in light and heavy water essentially disappear above the temperature of minimum solubility of the gases. The characteristic thermodynamic features of the aqueous solutions of gases (i.e., large values of -ΔS02 and of ΔC0p2) are still present at 520 K. It is shown that mean-field theories can account for the

Comparative Study of Two Different TiO2 Film Sensors on Response to H2 under UV Light and Room Temperature

PubMed Central

Peng, Xiaoying; Wang, Zhongming; Huang, Pan; Chen, Xun; Fu, Xianzhi; Dai, Wenxin

2016-01-01

An anatase TiO2 film sensor was prepared by a facile in-situ method on the interdigitated Au electrode deposited on the alumina substrate. The structure, morphology and the optical properties of the in-situ TiO2 film sensor were characterized by X-ray diffraction, Scanning Electron Microscopy, and UV-vis diffuse reflectance spectra. The photo-assisted gas sensitivities of the prepared film towards H2 gas were evaluated at room temperature in N2 and synthetic air atmospheres. As compared to TiO2 film sensor prepared by drop-coating method, this in-situ TiO2 film sensor exhibited a more compact structure composed of uniform TiO2 microspheres as well as a better gas sensitivity towards H2 under UV irradiation, especially in synthetic air. The photo-electrochemical measurements suggest that these improvements may be associated with the efficient charge transfer in the TiO2 interface induced by the TiO2 microsphere structure. This study might offer a feasible approach to develop photo-assisted gas sensors at ambient temperature. PMID:27509502

Experimental studies on cycling stable characteristics of inorganic phase change material CaCl2·6H2O-MgCl2·6H2O modified with SrCl2·6H2O and CMC

NASA Astrophysics Data System (ADS)

He, Meizhi; Yang, Luwei; Zhang, Zhentao

2018-01-01

By means of mass ratio method, binary eutectic hydrated salts inorganic phase change thermal energy storage system CaCl2·6H2O-20wt% MgCl2·6H2O was prepared, and through adding nucleating agent 1wt% SrCl2·6H2O and thickening agent 0.5wt% carboxy methyl cellulose (CMC), inoganic phase change material (PCM) modified was obtained. With recording cooling-melting curves simultaneously, this PCM was frozen and melted for 100 cycles under programmable temperature control. After per 10 cycles, the PCM was charaterized by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and density meter, then analysing variation characteristics of phase change temperature, supercooling degree, superheat degree, latent heat, crystal structure and density with the increase of cycle index. The results showed that the average values of average phase change temperature for cooling and heating process were 25.70°C and 27.39°C respectively with small changes. The average values of average supercooling and superheat degree were 0.59°C and 0.49°C respectively, and the maximum value was 1.10°C. The average value and standard deviation of latent heat of fusion were 120.62 J/g and 1.90 J/g respectively. Non-molten white solid sediments resulted from phase separation were tachyhydrite (CaMg2Cl6·12H2O), which was characterized by XRD. Measuring density of the PCM after per 10 cycles, and the results suggested that the total mass of tachyhydrite was limited. In summary, such modified inoganic PCM CaCl2·6H2O-20wt% MgCl2·6H2O-1wt% SrCl2·6H2O-0.5wt% CMC could stay excellent circulation stability within 100 cycles, and providing reference value in practical use.

Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

PubMed

Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

2016-09-13

Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols.

Phonon-mediated nuclear spin relaxation in H2O

NASA Astrophysics Data System (ADS)

Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

2017-03-01

A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

NASA Astrophysics Data System (ADS)

Foustoukos, D.; Mysen, B. O.

2011-12-01

Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

2017-10-01

O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

Water in Basaltic Melts: an Experimental and Thermodynamic Study of the Effect of H2O on Liquidus Temperatures.

NASA Astrophysics Data System (ADS)

Medard, E.; Grove, T. L.

2006-12-01

We present a thermodynamic model for the influence of H2O on liquidus temperatures of olivine-saturated primitive basaltic and andesitic melts. The thermodynamic model has been fitted to a suite of H2O-saturated liquidus experiments carried out on a primitive high-alumina basalt from Medicine Lake Volcano (82-72f) over a pressure range of 10 to 1000 MPa. The model of Silver and Stolper (S+S, 1985, J.Geol. 93:161) has been applied to the experimental data. This model uses the assumption of simple ideal mixing between water species and the anionic matrix in the melt. Water in the melt dissolves as molecular H2O, or dissociates to hydroxyl groups and an oxygen atomic network. For 82-72f, the liquidus olivine shows little compositional variability (Fo87.4 to Fo88.4) over the broad range of pressures and temperatures investigated that is not correlated with H2O content of the melt. This observation supports our assumption that major effect of H2O is on the anionic species in the melt and not on the cation equilibria (e.g. Mg and Si). The model reproduces the experimental data well. We find that there is a large influence of H2O addition on melting point for small amounts of H2O, resulting in a concave-down curvature when liquidus depression is plotted against the amount of H2O added. For addition of 0.8 and 5 wt% H2O to 82-72f, the liquidus is depressed by 35 K and 130 K, respectively. The best fits are obtained by assuming partial water dissociation to OH and H2O species, using the equilibrium constant measured by Stolper (1982). S+S applied their model to simple systems (diopside/H2O, albite/H2O, silica/H2O), and recovered the melting behavior extremely well. They also suggested that melt structure/composition influences the amount of liquidus depression caused by H2O addition. We have investigated the influence of bulk composition by performing complementary experiments on a high-magnesian andesite from Mount Shasta, and on a K, Na, and P rich alkali basalt from

Borate mineral assemblages in the system Na2OCaOMgOB2O3H2O

USGS Publications Warehouse

Christ, C.L.; Truesdell, A.H.; Erd, Richard C.

1967-01-01

he significant known hydrated borate mineral assemblages (principally of the western United States) in the system Na2OCaOz.sbnd;MgOB2O3H2O are expressible in three ternary composition diagrams. Phase rule interpretation of the diagrams is consistent with observation, if the activity of H2O is generally considered to be determined by the geologic environment. The absence of conflicting tie-lines on a diagram indicates that the several mineral assemblages of the diagram were formed under relatively narrow ranges of temperature and pressure. The known structural as well as empirical formulas for the minerals are listed, and the more recent (since 1960) crystal structure findings are discussed briefly. Schematic Gibbs free energy-composition diagrams based on known solubility-temperature relations in the systems Na2B4O7-H2O and Na2B4O7-NaCl-H2O, are highly useful in the interpretation and prediction of the stability relations in these systems; in particular these diagrams indicate clearly that tincalconite, although geologically important, is everywhere a metastable phase. Crystal-chemical considerations indicate that the same thermodynamic and kinetic behavior observed in the Na2B4O7-H2O system will hold in the Ca2B6O11-H2O system. This conclusion is confirmed by the petrologic evidence. The chemical relations among the mineral assemblages of a ternary diagram are expressed by a schematic "activity-activity" diagram. These activity-activity diagrams permit the tracing-out of the paragenetic sequences as a function of changing cation and H2O activities. ?? 1967.

Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

NASA Technical Reports Server (NTRS)

Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.;

N2/O2/H2 Dual-Pump Cars: Validation Experiments

NASA Technical Reports Server (NTRS)

OByrne, S.; Danehy, P. M.; Cutler, A. D.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

A novel ZrHIO6ṡ4H2O catalyst for degradation of organic dyes at room temperature

NASA Astrophysics Data System (ADS)

Li, Jiayin; Ma, Xinping; Qian, Meifan; Liu, Haoran; Liu, Qiying; Zhao, Caixian; Tian, Li; Chen, Lijuan; Tang, Jianting

It is interesting to obtain catalysts to degrade organic dye pollutants at room temperature for simultaneous purposes of environment-treating and energy-saving. In this work, a novel ZrHIO6ṡ4H2O catalyst was synthesized by reacting ZrO(NO3)2 with H5IO6 in aqueous nitric acid. The catalyst was found effective in degradation of rhodamine B (RhB) or methylene blue (MB) dyes at room temperature without light illumination. We used the ultraviolet-visible (UV-Vis) absorption spectra of dye solution as well as X-ray photoelectron spectroscopy (XPS) of ZrHIO6ṡ4H2O to confirm that the dye degradation was due to its catalytic role. Importantly, the ZrHIO6ṡ4H2O catalyst can be recycled five times without obvious activity loss and it achieved higher mineralization efficiency than the previously reported analogue in the degradation experiments.

Comparative study on the effect of H2 pre-adsorption on CO oxidation in O2-poor atmosphere over Au/TiO2 and TiO2: Temperature programmed surface reaction by a multiplexed mass spectrometer testing

NASA Astrophysics Data System (ADS)

Si, Ruiru; Liu, Junfeng; Zhang, Yujuan; Chen, Xun; Dai, Wenxin; Fu, Xianzhi

2016-11-01

The behaviors of H2 pre-adsorption on CO oxidation in an O2-poor stream containing a trace H2O over Au/TiO2 and TiO2 have been investigated by a temperature programmed surface reaction testing, respectively. It was found that the H2 pre-adsorption could keep CO oxidation without H2O consumption over Au/TiO2, but suppress CO oxidation over TiO2. The chemisorption testing showed that the H2 adsorption at Au/TiO2 could benefit to the formation of Ti-bonded hydroxyl species (Ti4+-OH), while the H2 adsorption at TiO2 would consume the Ti-bonded hydroxyl species and form the bridge hydroxyl species (Ti4+-OH-Ti4+). These results show that only the Ti-bonded hydroxyl species (not all kinds of hydroxyl species) could act as the active species of oxidizing CO. Furthermore, it is suggested that the dissociative hydrogen adsorbed at Au sites could activate the lattice oxygen of TiO2 to form the active Ti-bonded hydroxyl species (hydrogen spillover from Au to TiO2), which exhibit a strong reducibility than the H directly adsorbed at TiO2.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

NASA Astrophysics Data System (ADS)

Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-04-01

Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

NASA Astrophysics Data System (ADS)

Aranovich, L. Y.; Newton, R. C.

1996-10-01

H2O activities in concentrated NaCl solutions were measured in the ranges 600° 900° C and 2 15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)2) periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418 134.95 T(K). Using this function as a baseline, the experimental dehydration points in the system MgO-H2O-NaCl lead to a simple systematic relationship of high-temperature H2O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H2O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H2O, the H2O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl-H2O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary

Rapid food decomposition by H2O2-H2SO4 for determination of total mercury by flow injection cold vapor atomic absorption spectrometry.

PubMed

Zenebon, Odair; Sakuma, Alice M; Dovidauskas, Sergio; Okada, Isaura A; de, MaioFrancaD; Lichtig, Jaim

2002-01-01

A mixture of 50% H2O2-H2SO4 (3 + 1, v/v) was used for decomposition of food in open vessels at 80 degrees C. The treatment allowed rapid total mercury determination by flow injection cold vapor atomic absorption spectrometry. Cabbage, potatoes, peanuts paste, hazelnuts paste, oats, tomatoes and their derivatives, oysters, shrimps, prawns, shellfish, marine algae, and many kinds of fish were analyzed by the proposed methodology with a limit of quantitation of 0.86 +/- 0.08 microg/L mercury in the final solution. Reference materials tested also gave excellent recovery.

Probing the Release and Uptake of Water in α-MnO 2 · xH 2O

DOE PAGES

Yang, Zhenzhen; Ford, Denise C.; Park, Joong Sun; ...

2016-12-27

Alpha-MnO 2 is of interest as a cathode material for 3 V lithium batteries and as an electrode/electrocatalyst for higher energy, hybrid Li-ion/Li–O 2 systems. It has a structure with large tunnels that contain stabilizing cations such as Ba 2+, K + , NH 4 + , and H3O + (or water, H 2O). When stabilized by H 3O + /H 2O, the protons can be ion-exchanged with lithium to produce a Li 2O-stabilized α-MnO 2 structure. It has been speculated that the electrocatalytic process in Li–O 2 cells may be linked to the removal of lithium and oxygen frommore » the host α-MnO 2 structure during charge, and their reintroduction during discharge. In this investigation, hydrated α-MnO 2 was used, as a first step, to study the release and uptake of oxygen in α-MnO 2. Temperature-resolved in situ synchrotron X-ray diffraction (XRD) revealed a nonlinear, two-stage, volume change profile, which with the aide of X-ray absorption near-edge spectroscopy (XANES), redox titration, and density functional theory (DFT) calculations, is interpreted as the release of water from the α-MnO 2 tunnels. The two stages correspond to H 2O release from intercalated H 2O species at lower temperatures and H 3O + species at higher temperature. Thermogravimetric analysis confirmed the release of oxygen from α-MnO 2 in several stages during heating–including surface water, occluded water, and structural oxygen–and in situ UV resonance Raman spectroscopy corroborated the uptake and release of tunnel water by revealing small shifts in frequencies during the heating and cooling of α-MnO 2. Lastly, DFT calculations revealed the likelihood of disordered water species in binding sites in α-MnO 2 tunnels and a facile diffusion process.« less

Drying Temperature Dependence of Sol-gel Spin Coated Bilayer Composite ZnO/TiO2 Thin Films for Extended Gate Field Effect Transistor pH Sensor

NASA Astrophysics Data System (ADS)

Rahman, R. A.; Zulkefle, M. A.; Yusoff, K. A.; Abdullah, W. F. H.; Rusop, M.; Herman, S. H.

2018-03-01

This study presents an investigation on zinc oxide (ZnO) and titanium dioxide (TiO2) bilayer film applied as the sensing membrane for extended-gate field effect transistor (EGFET) for pH sensing application. The influences of the drying temperatures on the pH sensing capability of ZnO/TiO2 were investigated. The sensing performance of the thin films were measured by connecting the thin film to a commercial MOSFET to form the extended gates. By varying the drying temperature, we found that the ZnO/TiO2 thin film dried at 150°C gave the highest sensitivity compared to other drying conditions, with the sensitivity value of 48.80 mV/pH.

Improved hydrogen storage properties of MgH2 catalyzed with TiO2

NASA Astrophysics Data System (ADS)

Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

2018-05-01

In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

NASA Technical Reports Server (NTRS)

Kindler, Andrew; Huang, Yuhong

2010-01-01

Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

Melting temperatures of H2O up to 72 GPa measured in a diamond anvil cell using CO2 laser heating technique.

PubMed

Kimura, T; Kuwayama, Y; Yagi, T

2014-02-21

The melting curve of H2O from 49 to 72 GPa was determined by using a laser-heated diamond anvil cell. Double-sided CO2 laser heating technique was employed in order to heat the sample directly. Discontinuous changes of the heating efficiency attributed to the H2O melting were observed between 49 and 72 GPa. The obtained melting temperatures at 49 and 72 GPa are 1200 and 1410 K, respectively. We found that the slope of the melting curve significantly decreases with increasing pressure, only 5 K/GPa at 72 GPa while 44 K/GPa at 49 GPa. Our results suggest that the melting curve does not intersect with the isentropes of Uranus and Neptune, and hence, H2O should remain in the liquid state even at the pressure and temperature conditions found deep within Uranus and Neptune.

Application of TAED/H2O2 system for low temperature bleaching of crude cellulose extracted from jute fiber

NASA Astrophysics Data System (ADS)

Wen, Zuoqiang; Zou, Linbo; Wang, Weiming

2018-03-01

Tetraacetylethylenediamine (TAED) activated hydrogen peroxide system had been applied for bleaching of crude cellulose extracted from jute fiber. Comparing with conventional hydrogen peroxide bleaching system, those results showed that bleaching temperature and time could be effectively reduced, and a preferable whiteness could be produced under faint alkaline condition. And the optimum conditions for activated bleaching system could be summarized as molar ratio of H2O2/TAED 1:0.7, pH 8, pure hydrogen peroxide 0.09 mol/L, temperature 70 °C and time 60min.

Quantitative agreement between [(15)O]H2O PET and model free QUASAR MRI-derived cerebral blood flow and arterial blood volume.

PubMed

Heijtel, D F R; Petersen, E T; Mutsaerts, H J M M; Bakker, E; Schober, P; Stevens, M F; van Berckel, B N M; Majoie, C B L M; Booij, J; van Osch, M J P; van Bavel, E T; Boellaard, R; Lammertsma, A A; Nederveen, A J

2016-04-01

The purpose of this study was to assess whether there was an agreement between quantitative cerebral blood flow (CBF) and arterial cerebral blood volume (CBVA) measurements by [(15)O]H2O positron emission tomography (PET) and model-free QUASAR MRI. Twelve healthy subjects were scanned within a week in separate MRI and PET imaging sessions, after which quantitative and qualitative agreement between both modalities was assessed for gray matter, white matter and whole brain region of interests (ROI). The correlation between CBF measurements obtained with both modalities was moderate to high (r(2): 0.28-0.60, P < 0.05), although QUASAR significantly underestimated CBF by 30% (P < 0.001). CBVA was moderately correlated (r(2): 0.28-0.43, P < 0.05), with QUASAR yielding values that were only 27% of the [(15)O]H2O-derived values (P < 0.001). Group-wise voxel statistics identified minor areas with significant contrast differences between [(15)O]H2O PET and QUASAR MRI, indicating similar qualitative CBVA and CBF information by both modalities. In conclusion, the results of this study demonstrate that QUASAR MRI and [(15)O]H2O PET provide similar CBF and CBVA information, but with systematic quantitative discrepancies. Copyright © 2016 John Wiley & Sons, Ltd.

An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

NASA Astrophysics Data System (ADS)

Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

2012-12-01

strength of hydrogen bonding of the H2O molecules in microporous silicates does not appear to change greatly with decreasing temperatures from 300 K down to 10 K. The reason for this and also understanding better the ion-dipole interaction and its effect on H-bonding strength in Ca-quasi clusters need further study. The crystal structure of armenite viewed down [001] and [010].

OH and O radicals production in atmospheric pressure air/Ar/H2O gliding arc discharge plasma jet

NASA Astrophysics Data System (ADS)

N, C. ROY; M, R. TALUKDER; A, N. CHOWDHURY

2017-12-01

Atmospheric pressure air/Ar/H2O gliding arc discharge plasma is produced by a pulsed dc power supply. An optical emission spectroscopic (OES) diagnostic technique is used for the characterization of plasmas and for identifications of {{OH}} and {{O}} radicals along with other species in the plasmas. The OES diagnostic technique reveals the excitation T x ≈ 5550-9000 K, rotational T r ≈ 1350-2700 K and gas T g ≈ 850-1600 K temperatures, and electron density {n}{{e}}≈ ({1.1-1.9})× {10}14 {{{cm}}}-3 under different experimental conditions. The production and destruction of {{OH}} and {{O}} radicals are investigated as functions of applied voltage and air flow rate. Relative intensities of {{OH}} and {{O}} radicals indicate that their production rates are increased with increasing {{Ar}} content in the gas mixture and applied voltage. {n}{{e}} reveals that the higher densities of {{OH}} and {{O}} radicals are produced in the discharge due to more effective electron impact dissociation of {{{H}}}2{{O}} and {{{O}}}2 molecules caused by higher kinetic energies as gained by electrons from the enhanced electric field as well as by enhanced {n}{{e}}. The productions of {{OH}} and {{O}} are decreasing with increasing air flow rate due to removal of Joule heat from the discharge region but enhanced air flow rate significantly modifies discharge maintenance properties. Besides, {T}{{g}} significantly reduces with the enhanced air flow rate. This investigation reveals that {{Ar}} plays a significant role in the production of {{OH}} and {{O}} radicals.

Ab Initio Reaction Kinetics of CH 3 O$$\\dot{C}$$(=O) and $$\\dot{C}$$H 2 OC(=O)H Radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Ting; Yang, Xueliang; Ju, Yiguang

The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3Omore » $$\\dot{C}$$(=O)) and (formyloxy)methyl radical ($$\\dot{C}$$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$$\\dot{C}$$(=O) to $$\\dot{C}$$H3 and CO2 is predicted to be much faster than dissociating to CH3$$\\dot{O}$$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$$\\dot{C}$$(=O) and $$\\dot{C}$$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$$\\dot{O}$$ removal mechanisms under atmospheric conditions, the reaction kinetics of

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

PubMed Central

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow.

PubMed

Al-Rasheed, Radwan; Cardin, David J

2003-06-01

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).

Resonant tunneling modulation in quasi-2D Cu2O/SnO2 p-n horizontal-multi-layer heterostructure for room temperature H2S sensor application

PubMed Central

Cui, Guangliang; Zhang, Mingzhe; Zou, Guangtian

2013-01-01

Heterostructure material that acts as resonant tunneling system is a major scientific challenge in applied physics. Herein, we report a resonant tunneling system, quasi-2D Cu2O/SnO2 p-n heterostructure multi-layer film, prepared by electrochemical deposition in a quasi-2D ultra-thin liquid layer. By applying a special half-sine deposition potential across the electrodes, Cu2O and SnO2 selectively and periodically deposited according to their reduction potentials. The as-prepared heterostructure film displays excellent sensitivity to H2S at room temperature due to the resonant tunneling modulation. Furthermore, it is found that the laser illumination could enhance the gas response, and the mechanism with laser illumination is discussed. It is the first report on gas sensing application of resonant tunneling modulation. Hence, heterostructure material act as resonant tunneling system is believed to be an ideal candidate for further improvement of room temperature gas sensing. PMID:23409241

Resonant tunneling modulation in quasi-2D Cu(2)O/SnO(2) p-n horizontal-multi-layer heterostructure for room temperature H(2)S sensor application.

PubMed

Cui, Guangliang; Zhang, Mingzhe; Zou, Guangtian

2013-01-01

Heterostructure material that acts as resonant tunneling system is a major scientific challenge in applied physics. Herein, we report a resonant tunneling system, quasi-2D Cu(2)O/SnO(2) p-n heterostructure multi-layer film, prepared by electrochemical deposition in a quasi-2D ultra-thin liquid layer. By applying a special half-sine deposition potential across the electrodes, Cu(2)O and SnO(2) selectively and periodically deposited according to their reduction potentials. The as-prepared heterostructure film displays excellent sensitivity to H(2)S at room temperature due to the resonant tunneling modulation. Furthermore, it is found that the laser illumination could enhance the gas response, and the mechanism with laser illumination is discussed. It is the first report on gas sensing application of resonant tunneling modulation. Hence, heterostructure material act as resonant tunneling system is believed to be an ideal candidate for further improvement of room temperature gas sensing.

Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

Investigation on the mode of AC discharge in H2O affected by temperature

NASA Astrophysics Data System (ADS)

Siyuan, DONG; Shaomeng, GUO; Dan, WEN; Xiaoliang, TANG; Gao, QIU

2018-04-01

In this paper, some experimental equipment has been set up for kHz frequency AC liquid phase discharge, and the temperature of the deionized water was regulated during discharge. The electrical characteristics and spectra of liquid phase H2O discharge have been investigated. Two discharge modes, high temperature and low temperature, were both found. The results show that there are two mechanisms in liquid phase discharge: the field ionization mechanism and the breakdown mechanism of bubbles, and these two mechanisms are always developed simultaneously; the temperature is the key factor determining the discharge type. At high temperature, the breakdown of bubbles is the main discharge mechanism, and the field ionization mechanism occurs mainly at low temperature.

Dynamics and unsteady morphologies at ice interfaces driven by D2O–H2O exchange

PubMed Central

Holmes-Cerfon, Miranda; Kohn, Robert V.

2017-01-01

The growth dynamics of D2O ice in liquid H2O in a microfluidic device were investigated between the melting points of D2O ice (3.8 °C) and H2O ice (0 °C). As the temperature was decreased at rates between 0.002 °C/s and 0.1 °C/s, the ice front advanced but retreated immediately upon cessation of cooling, regardless of the temperature. This is a consequence of the competition between diffusion of H2O into the D2O ice, which favors melting of the interface, and the driving force for growth supplied by cooling. Raman microscopy tracked H/D exchange across the solid H2O–solid D2O interface, with diffusion coefficients consistent with transport of intact H2O molecules at the D2O ice interface. At fixed temperatures below 3 °C, the D2O ice front melted continuously, but at temperatures near 0 °C a scalloped interface morphology appeared with convex and concave sections that cycled between growth and retreat. This behavior, not observed for D2O ice in contact with D2O liquid or H2O ice in contact with H2O liquid, reflects a complex set of cooperative phenomena, including H/D exchange across the solid–liquid interface, latent heat exchange, local thermal gradients, and the Gibbs–Thomson effect on the melting points of the convex and concave features. PMID:29042511

Interfacial RhO{sub x}/CeO{sub 2} sites as locations for low temperature N{sub 2}O dissociation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cunningham, J.; Hickey, J.N.; Soria, J.

Temperatures required for extensive N{sub 2}O dissociation to N{sub 2}, or to N{sub 2} plus O{sub 2}, over 0.5% RhO{sub x}/CeO{sub 2} materials, and over polycrystalline Rh{sub 2}O{sub 3} or CeO{sub 2}, are compared for preoxidised and for prereduced samples on the basis of conversions achieved in pulsed-reactant, continuous-flow and recirculatory microcatalytic reactors. Influences of sample prereduction or preoxidation upon those measurements and upon results from parallel ESR and FTIR studies of N{sub 2}O interactions with such materials are presented and compared. Over partially reduced 0.5% RhO{sub x}/CeO{sub 2} materials complete dissociation of N{sub 2}O pulses to N{sub 2} plusmore » O{sub 2} is obtained at temperatures 50-100{degrees} lower than those required for extensive dissociation over prereduced Rh{sub 2}O{sub 3}. Furthermore, N{sub 2} was the sole product from the latter. Higher ongoing N{sub 2}O conversions to N{sub 2} plus O{sub 2} at 623 K over 0.5% Rh/CeO{sub 2} in pulsed-reactant than in continuous-flow mode point to regeneration of active sites under helium flushing between pulses. The TPD profile for dioxygen release from Rhodia containing samples at temperatures 350-550 K is presented. ESR measurements reveal complementary effects of outgassings at temperatures, T{sub v}, {ge} 573 K upon the availability at RhO{sub x}/CeO{sub 2} surfaces of electron-excess sites reactive towards N{sub 2}O. Differences from observations over Rh{sub 2}O{sub 3} and CeO{sub 2} can be understood by attributing the low-temperature activity of RhO{sub x}/CeO{sub 2} to electron excess sites at microinterfaces between the dispersed Rhodia component and the Ceria support.« less

Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers

NASA Technical Reports Server (NTRS)

Bellan, Josette; Harstad, Kenneth; Okong'o, Nora

2003-01-01

This report presents a study of numerical simulations of mixing layers developing between opposing flows of paired fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence. The simulations were performed for two different fluid pairs O2/H2 and C7H16/N2 at similar reduced initial pressures (reduced pressure is defined as pressure divided by critical pressure). Thermodynamically, O2/H2 behaves more nearly like an ideal mixture and has greater solubility, relative to C7H16/N2, which departs strongly from ideality. Because of a specified smaller initial density stratification, the C7H16/N2 layers exhibited greater levels of growth, global molecular mixing, and turbulence. However, smaller density gradients at the transitional state for the O2/H2 system were interpreted as indicating that locally, this system exhibits enhanced mixing as a consequence of its greater solubility and closer approach to ideality. These thermodynamic features were shown to affect entropy dissipation, which was found to be larger for O2/H2 and concentrated in high-density-gradient-magnitude regions that are distortions of the initial density-stratification boundary. In C7H16/N2, the regions of largest dissipation were found to lie in high-density-gradient-magnitude regions that result from mixing of the two fluids.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Spectral and thermal studies of MgI2·8H2O

NASA Astrophysics Data System (ADS)

Koleva, Violeta; Stefov, Viktor; Najdoski, Metodija; Ilievski, Zlatko; Cahil, Adnan

2017-10-01

In the present contribution special attention is paid to the spectroscopic and thermal characterization of MgI2·8H2O which is the stable hydrated form at room temperature. The infrared spectra of MgI2·8H2O and its deuterated analogues recorded at room and liquid nitrogen temperature are presented and interpreted. In the low-temperature diference infrared spectrum of the slightly deuterated analogue (≈5% D) at least four bands are found out of the expected five (at 2595, 2550, 2538 and 2495 cm-1) as a result of the uncoupled O-D oscillators in the isotopically isolated HOD molecules. Multiple bands are observed in the water bending region and only two bands of the HOH librational modes are found. For more precise and deep description of the processes occurring upon heating of MgI2·8H2O we have applied simultaneous TG/DTA/Mass spectrometry technique identifying the gases evolved during the thermal transformations. We have established that the thermal decomposition of MgI2·8H2O is a complex process that takes place in two main stages. In the first stage (between 120 and 275 °C) the salt undergoes a partial stepwise dehydration to MgI2·2H2O followed by a hydrolytic decomposition with formation of magnesium hydroxyiodide Mg(OH)1.44I0.56 accompanied with simultaneous release of H2O and HI. In the second stage Mg(OH)1.44I0.56 is completely decomposed to MgO with elimination of gaseous H2O, HI, I2 and H2. Infrared spectra of the annealed samples heated between 190 and 270 °C confirmed the formation of magnesium hydroxyiodide.

Concurrent separation of CO2 and H2O from air by a temperature-vacuum swing adsorption/desorption cycle.

PubMed

Wurzbacher, Jan Andre; Gebald, Christoph; Piatkowski, Nicolas; Steinfeld, Aldo

2012-08-21

A temperature-vacuum swing (TVS) cyclic process is applied to an amine-functionalized nanofibrilated cellulose sorbent to concurrently extract CO(2) and water vapor from ambient air. The promoting effect of the relative humidity on the CO(2) capture capacity and on the amount of coadsorbed water is quantified. The measured specific CO(2) capacities range from 0.32 to 0.65 mmol/g, and the corresponding specific H(2)O capacities range from 0.87 to 4.76 mmol/g for adsorption temperatures varying between 10 and 30 °C and relative humidities varying between 20 and 80%. Desorption of CO(2) is achieved at 95 °C and 50 mbar(abs) without dilution by a purge gas, yielding a purity exceeding 94.4%. Sorbent stability and a closed mass balance for both H(2)O and CO(2) are demonstrated for ten consecutive adsorption-desorption cycles. The specific energy requirements of the TVS process based on the measured H(2)O and CO(2) capacities are estimated to be 12.5 kJ/mol(CO2) of mechanical (pumping) work and between 493 and 640 kJ/mol(CO2) of heat at below 100 °C, depending on the air relative humidity. For a targeted CO(2) capacity of 2 mmol/g, the heat requirement would be reduced to between 272 and 530 kJ/mol(CO2), depending strongly on the amount of coadsorbed water.

The renal blood flow reserve in healthy humans and patients with atherosclerotic renovascular disease measured by positron emission tomography using [15O]H2O.

PubMed

Päivärinta, Johanna; Koivuviita, Niina; Oikonen, Vesa; Iida, Hidehiro; Liukko, Kaisa; Manner, Ilkka; Löyttyniemi, Eliisa; Nuutila, Pirjo; Metsärinne, Kaj

2018-06-11

Microvascular function plays an important role in ARVD (atherosclerotic renovascular disease). RFR (renal flow reserve), the capacity of renal vasculature to dilate, is known to reflect renal microvascular function. In this pilot study, we assessed PET (positron emission tomography)-based RFR values of healthy persons and renal artery stenosis patients. Seventeen patients with ARVD and eight healthy subjects were included in the study. Intravenous enalapril 1 mg was used as a vasodilatant, and the maximum response (blood pressure and RFR) to it was measured at 40 min. Renal perfusion was measured by means of oxygen-15-labeled water PET. RFR was calculated as a difference of stress flow and basal flow and was expressed as percent [(stress blood flow - basal blood flow)/basal blood flow] × 100%. RFR of the healthy was 22%. RFR of the stenosed kidneys of bilateral stenosis patients (27%) was higher than that of the stenosed kidneys of unilateral stenosis patients (15%). RFR of the contralateral kidneys of unilateral stenosis patients was 21%. There was no difference of statistical significance between RFR values of ARVD subgroups or between ARVD subgroups and the healthy. In the stenosed kidneys of unilateral ARVD patients, stenosis grade of the renal artery correlated negatively with basal (p = 0.04) and stress flow (p = 0.02). Dispersion of RFR values was high. This study is the first to report [ 15 O]H 2 O PET-based RFR values of healthy subjects and ARVD patients in humans. The difference between RFR values of ARVD patients and the healthy did not reach statistical significance perhaps because of high dispersion of RFR values. [ 15 O]H 2 O PET is a valuable non-invasive and quantitative method to evaluate renal blood flow though high dispersion makes imaging challenging. Larger studies are needed to get more information about [ 15 O]H 2 O PET method in evaluation of renal blood flow.

Room-temperature NaI/H2O compression icing: solute-solute interactions.

PubMed

Zeng, Qingxin; Yao, Chuang; Wang, Kai; Sun, Chang Q; Zou, Bo

2017-10-11

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H 2 O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures P C1 and P C2 , for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the P C1 faster than the P C2 that remains almost constant at higher NaI/H 2 O molecular number ratios. Concentration increase moves the P C1 along the liquid-VI phase boundary and it finally merges with P C2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H 2 O concentration from that of the solute type at an identical concentration on the phase transitions.

Novel Process of Simultaneous Removal of Nitric Oxide and Sulfur Dioxide Using a Vacuum Ultraviolet (VUV)-Activated O2/H2O/H2O2 System in A Wet VUV-Spraying Reactor.

PubMed

Liu, Yangxian; Wang, Qian; Pan, Jianfeng

2016-12-06

A novel process for NO and SO 2 simultaneous removal using a vacuum ultraviolet (VUV, with 185 nm wavelength)-activated O 2 /H 2 O/H 2 O 2 system in a wet VUV-spraying reactor was developed. The influence of different process variables on NO and SO 2 removal was evaluated. Active species (O 3 and ·OH) and liquid products (SO 3 2- , NO 2 - , SO 4 2- , and NO 3 - ) were analyzed. The chemistry and routes of NO and SO 2 removal were investigated. The oxidation removal system exhibits excellent simultaneous removal capacity for NO and SO 2 , and a maximum removal of 96.8% for NO and complete SO 2 removal were obtained under optimized conditions. SO 2 reaches 100% removal efficiency under most of test conditions. NO removal is obviously affected by several process variables. Increasing VUV power, H 2 O 2 concentration, solution pH, liquid-to-gas ratio, and O 2 concentration greatly enhances NO removal. Increasing NO and SO 2 concentration obviously reduces NO removal. Temperature has a dual impact on NO removal, which has an optimal temperature of 318 K. Sulfuric acid and nitric acid are the main removal products of NO and SO 2 . NO removals by oxidation of O 3 , O·, and ·OH are the primary routes. NO removals by H 2 O 2 oxidation and VUV photolysis are the complementary routes. A potential scaled-up removal process was also proposed initially.

A model-based understanding of solid-oxide electrolysis cells (SOECs) for syngas production by H2O/CO2 co-electrolysis

NASA Astrophysics Data System (ADS)

Menon, Vikram; Fu, Qingxi; Janardhanan, Vinod M.; Deutschmann, Olaf

2015-01-01

High temperature co-electrolysis of H2O and CO2 offers a promising route for syngas (H2, CO) production via efficient use of heat and electricity. The performance of a SOEC during co-electrolysis is investigated by focusing on the interactions between transport processes and electrochemical parameters. Electrochemistry at the three-phase boundary is modeled by a modified Butler-Volmer approach that considers H2O electrolysis and CO2 electrolysis, individually, as electrochemically active charge transfer pathways. The model is independent of the geometrical structure. A 42-step elementary heterogeneous reaction mechanism for the thermo-catalytic chemistry in the fuel electrode, the dusty gas model (DGM) to account for multi-component diffusion through porous media, and a plug flow model for flow through the channels are used in the model. Two sets of experimental data are reproduced by the simulations, in order to deduce parameters of the electrochemical model. The influence of micro-structural properties, inlet cathode gas velocity, and temperature are discussed. Reaction flow analysis is performed, at OCV, to study methane production characteristics and kinetics during co-electrolysis. Simulations are carried out for configurations ranging from simple one-dimensional electrochemical button cells to quasi-two-dimensional co-flow planar cells, to demonstrate the effectiveness of the computational tool for performance and design optimization.

Measured Fluid Flow in an Active H2O-CO2 Geothermal Well as an Analog to Fluid Flow in Fractures on Mars: Preliminary Report

NASA Technical Reports Server (NTRS)

Kieffer, Susan W.; Brown, K. L.; Simmons, Stuart F.; Watson, Arnold

2004-01-01

Water in the Earth's crust generally contains dissolved gases such as CO2. Models for both 'Blue Mars' (H2O-driven processes) and 'White Mars' (CO2-driven processes) predict liquid H2O with dissolved CO2 at depth. The fate of dissolved CO2 as this mixture rises toward the surface has not been quantitatively explored. Our approach is a variation on NASA's 'Follow the Water' as we 'Follow the Fluid' from depth to the surface in hydrothermal areas on Earth and extrapolate our results to Mars. This is a preliminary report on a field study of fluid flow in a producing geothermal well. For proprietary reasons, the name and location of this well cannot be revealed, so we have named it 'Earth1' for this study.

Physical limit of stability in supercooled D2O and D2O+H2O mixtures

NASA Astrophysics Data System (ADS)

Kiselev, S. B.; Ely, J. F.

2003-01-01

The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

Electron-temperature dependence of the recombination of H3O+(H2O)n ions with electrons

NASA Technical Reports Server (NTRS)

Johnsen, R.

1993-01-01

The T(e) dependence of the recombination of H3O+(H2O)n cluster-ions with electrons has been measured in an afterglow experiment in which the electrons were heated by a radio-frequency electric field. The recombination coefficients were found to vary with T(e) as about T(e) exp -1/2 in better agreement with theoretical expectations than earlier results of microwave-afterglow measurements.

Helicity in Supercritical O2/H2 and C7H16/N2 Mixing Layers

NASA Technical Reports Server (NTRS)

Okongo, Nora; Bellan, Josette

2004-01-01

This report describes a study of databases produced by direct numerical simulation of mixing layers developing between opposing flows of two fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence, with emphasis on helicity. The simulations were performed for two different fluid pairs -- O2/H2 and C7H16/N2 -- at similar values of reduced pressure.

Simultaneous Online Measurement of H2O and CO2 in the Humid CO2 Adsorption/Desorption Process.

PubMed

Yu, Qingni; Ye, Sha; Zhu, Jingke; Lei, Lecheng; Yang, Bin

2015-01-01

A dew point meter (DP) and an infrared (IR) CO2 analyzer were assembled in a humid CO2 adsorption/desorption system in series for simultaneous online measurements of H2O and CO2, respectively. The humidifier, by using surface-flushing on a saturated brine solution was self-made for the generation of humid air flow. It was found that by this method it became relatively easy to obtain a low H2O content in air flow and that its fluctuation could be reduced compared to the bubbling method. Water calibration for the DP-IR detector is necessary to be conducted for minimizing the measurement error of H2O. It demonstrated that the relative error (RA) for simultaneous online measurements H2O and CO2 in the desorption process is lower than 0.1%. The high RA in the adsorption of H2O is attributed to H2O adsorption on the transfer pipe and amplification of the measurement error. The high accuracy of simultaneous online measurements of H2O and CO2 is promising for investigating their co-adsorption/desorption behaviors, especially for direct CO2 capture from ambient air.

Crystalline and amorphous H2O on Charon

NASA Astrophysics Data System (ADS)

Dalle Ore, Cristina M.; Cruikshank, Dale P.; Grundy, Will M.; Ennico, Kimberly; Olkin, Catherine B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.

2015-11-01

Charon, the largest satellite of Pluto, is a gray-colored icy world covered mostly in H2O ice, with spectral evidence for NH3, as previously reported (Cook et al. 2007, Astrophys. J. 663, 1406-1419 Merlin, et al. 2010, Icarus, 210, 930; Cook, et al. 2014, AAS/Division for Planetary Sciences Meeting Abstracts, 46, #401.04). Images from the New Horizons spacecraft reveal a surface with terrains of widely different ages and a moderate degree of localized coloration. The presence of H2O ice in its crystalline form (Brown & Calvin 2000 Science 287, 107-109; Buie & Grundy 2000 Icarus 148, 324-339; Merlin et al, 2010) along with NH3 is consistent with a fresh surface.The phase of H2O ice is a key tracer of variations in temperature and physical conditions on the surface of outer Solar System objects. At Charon’s surface temperature H2O is expected to be amorphous, but ground-based observations (e.g., Merlin et al. 2010) show a clearly crystalline signature. From laboratory experiments it is known that amorphous H2O ice becomes crystalline at temperatures of ~130 K. Other mechanisms that can change the phase of the ice from amorphous to crystalline include micro-meteoritic bombardment (Porter et al. 2010, Icarus, 208, 492) or resurfacing processes such as cryovolcanism.New Horizons observed Charon with the LEISA imaging spectrometer, part of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Science Reviews, 140, 129). Making use of high spatial resolution (better than 10 km/px) and spectral resolving power of 240 in the wavelength range 1.25-2.5 µm, and 560 in the range 2.1-2.25 µm, we report on an analysis of the phase of H2O ice on parts of Charon’s surface with a view to investigate the recent history and evolution of this small but intriguing object.This work was supported by NASA’s New Horizons project.

The effect of rock particles and D2O replacement on the flow behaviour of ice.

PubMed

Middleton, Ceri A; Grindrod, Peter M; Sammonds, Peter R

2017-02-13

Ice-rock mixtures are found in a range of natural terrestrial and planetary environments. To understand how flow processes occur in these environments, laboratory-derived properties can be extrapolated to natural conditions through flow laws. Here, deformation experiments have been carried out on polycrystalline samples of pure ice, ice-rock and D 2 O-ice-rock mixtures at temperatures of 263, 253 and 233 K, confining pressure of 0 and 48 MPa, rock fraction of 0-50 vol.% and strain-rates of 5 × 10 -7 to 5 × 10 -5  s -1 Both the presence of rock particles and replacement of H 2 O by D 2 O increase bulk strength. Calculated flow law parameters for ice and H 2 O-ice-rock are similar to literature values at equivalent conditions, except for the value of the rock fraction exponent, here found to be 1. D 2 O samples are 1.8 times stronger than H 2 O samples, probably due to the higher mass of deuterons when compared with protons. A gradual transition between dislocation creep and grain-size-sensitive deformation at the lowest strain-rates in ice and ice-rock samples is suggested. These results demonstrate that flow laws can be found to describe ice-rock behaviour, and should be used in modelling of natural processes, but that further work is required to constrain parameters and mechanisms for the observed strength enhancement.This article is part of the themed issue 'Microdynamics of ice'. © 2016 The Author(s).

The effect of rock particles and D2O replacement on the flow behaviour of ice

PubMed Central

Grindrod, Peter M.

2017-01-01

Ice–rock mixtures are found in a range of natural terrestrial and planetary environments. To understand how flow processes occur in these environments, laboratory-derived properties can be extrapolated to natural conditions through flow laws. Here, deformation experiments have been carried out on polycrystalline samples of pure ice, ice–rock and D2O-ice–rock mixtures at temperatures of 263, 253 and 233 K, confining pressure of 0 and 48 MPa, rock fraction of 0–50 vol.% and strain-rates of 5 × 10−7 to 5 × 10−5 s−1. Both the presence of rock particles and replacement of H2O by D2O increase bulk strength. Calculated flow law parameters for ice and H2O-ice–rock are similar to literature values at equivalent conditions, except for the value of the rock fraction exponent, here found to be 1. D2O samples are 1.8 times stronger than H2O samples, probably due to the higher mass of deuterons when compared with protons. A gradual transition between dislocation creep and grain-size-sensitive deformation at the lowest strain-rates in ice and ice–rock samples is suggested. These results demonstrate that flow laws can be found to describe ice–rock behaviour, and should be used in modelling of natural processes, but that further work is required to constrain parameters and mechanisms for the observed strength enhancement. This article is part of the themed issue ‘Microdynamics of ice’. PMID:28025298

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

NASA Technical Reports Server (NTRS)

Copland, Evan; Myers, Dwight; Opila, Elizabeth J.; Jacobson, Nathan S.

2001-01-01

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2(111)

DOE PAGES

Sutton, Jonathan E.; Danielson, Thomas; Beste, Ariana; ...

2017-11-14

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is amore » naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.« less

Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, Jonathan E.; Danielson, Thomas; Beste, Ariana

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is amore » naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.« less

H2O Adsorption Kinetics on Smectites

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard C.; Howard, Jeanie; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The adsorptive equilibration of H2O a with montomorillonite, a smectite clay has been measured. At low temperatures and pressures, equilibration can require many hours, effectively preventing smectites at the martian surface from responding rapidly to diurnal pressure and temperature variations.

Quantification of myocardial blood flow with 11C-hydroxyephedrine dynamic PET: comparison with 15O-H2O PET.

PubMed

Hiroshima, Yuji; Manabe, Osamu; Naya, Masanao; Tomiyama, Yuuki; Magota, Keiichi; Obara, Masahiko; Aikawa, Tadao; Oyama-Manabe, Noriko; Yoshinaga, Keiichiro; Hirata, Kenji; Kroenke, Markus; Tamaki, Nagara; Katoh, Chietsugu

2017-12-21

11 C-hydroxyephedrine (HED) PET has been used to evaluate the myocardial sympathetic nervous system (SNS). Here we sought to establish a simultaneous approach for quantifying both myocardial blood flow (MBF) and the SNS from a single HED PET scan. Ten controls and 13 patients with suspected cardiac disease were enrolled. The inflow rate of 11 C-HED (K1) was obtained using a one-tissue-compartment model. We compared this rate with the MBF derived from 15 O-H 2 O PET. In the controls, the relationship between K 1 from 11 C-HED PET and the MBF from 15 O-H 2 O PET was linked by the Renkin-Crone model. The relationship between K 1 from 11 C-HED PET and the MBF from 15 O-H 2 O PET from the controls' data was approximated as follows: K 1   =  (1 - 0.891 * exp(- 0.146/MBF)) * MBF. In the validation set, the correlation coefficient demonstrated a significantly high relationship for both the whole left ventricle (r = 0.95, P < 0.001) and three coronary territories (left anterior descending artery: r = 0.96, left circumflex artery: r = 0.81, right coronary artery: r =  0.86; P < 0.001, respectively). 11 C-HED can simultaneously estimate MBF and sympathetic nervous function without requiring an additional MBF scan for assessing mismatch areas between MBF and SNS.

Influence of hydroxyapatite nanoparticles on the viscosity of dimethyl sulfoxide-H2O-NaCl and glycerol-H2O-NaCl ternary systems at subzero temperatures.

PubMed

Yi, Jingru; Tang, Heyu; Zhao, Gang

2014-10-01

The viscosity, at subzero temperatures, of ternary solutions commonly used in cryopreservation is tremendously important for understanding ice formation and molecular diffusion in biopreservation. However, this information is scarce in the literature. In addition, to the best of our knowledge, the effect of nanoparticles on the viscosity of these solutions has not previously been reported. The objectives of this study were thus: (i) to systematically measure the subzero viscosity of two such systems, dimethyl sulfoxide (Me2SO)-H2O-NaCl and glycerol-H2O-NaCl; (ii) to explore the effect of hydroxyapatite (HA) nanoparticles on the viscosity; and (iii) to provide models that precisely predict viscosity at multiple concentrations of cryoprotective agent (CPA) in saline solutions at subzero temperatures. Our experiments were performed in two parts. We first measured the viscosity at multiple CPA concentrations [0.3-0.75 (w/w)] in saline solution with and without nanoparticles at subzero temperatures (0 to -30°C). The data exhibited a good fit to the Williams-Landel-Ferry (WLF) equation. We then measured the viscosity of residual unfrozen ternary solutions with and without nanoparticles during equilibrium freezing. HA nanoparticles made the solution more viscous, suggesting applications for these nanoparticles in preventing cell dehydration, ice nucleation, and ice growth during freezing and thawing in cryopreservation. Copyright © 2014 Elsevier Inc. All rights reserved.

Room temperature CO and H2 sensing with carbon nanoparticles.

PubMed

Kim, Daegyu; Pikhitsa, Peter V; Yang, Hongjoo; Choi, Mansoo

2011-12-02

We report on a shell-shaped carbon nanoparticle (SCNP)-based gas sensor that reversibly detects reducing gas molecules such as CO and H(2) at room temperature both in air and inert atmosphere. Crystalline SCNPs were synthesized by laser-assisted reactions in pure acetylene gas flow, chemically treated to obtain well-dispersed SCNPs and then patterned on a substrate by the ion-induced focusing method. Our chemically functionalized SCNP-based gas sensor works for low concentrations of CO and H(2) at room temperature even without Pd or Pt catalysts commonly used for splitting H(2) molecules into reactive H atoms, while metal oxide gas sensors and bare carbon-nanotube-based gas sensors for sensing CO and H(2) molecules can operate only at elevated temperatures. A pristine SCNP-based gas sensor was also examined to prove the role of functional groups formed on the surface of functionalized SCNPs. A pristine SCNP gas sensor showed no response to reducing gases at room temperature but a significant response at elevated temperature, indicating a different sensing mechanism from a chemically functionalized SCNP sensor.

Submillimeter H2O and H2O+emission in lensed ultra- and hyper-luminous infrared galaxies at z 2-4

NASA Astrophysics Data System (ADS)

Yang, C.; Omont, A.; Beelen, A.; González-Alfonso, E.; Neri, R.; Gao, Y.; van der Werf, P.; Weiß, A.; Gavazzi, R.; Falstad, N.; Baker, A. J.; Bussmann, R. S.; Cooray, A.; Cox, P.; Dannerbauer, H.; Dye, S.; Guélin, M.; Ivison, R.; Krips, M.; Lehnert, M.; Michałowski, M. J.; Riechers, D. A.; Spaans, M.; Valiante, E.

2016-11-01

We report rest-frame submillimeter H2O emission line observations of 11 ultra- or hyper-luminous infrared galaxies (ULIRGs or HyLIRGs) at z 2-4 selected among the brightest lensed galaxies discovered in the Herschel-Astrophysical Terahertz Large Area Survey (H-ATLAS). Using the IRAM NOrthern Extended Millimeter Array (NOEMA), we have detected 14 new H2O emission lines. These include five 321-312ortho-H2O lines (Eup/k = 305 K) and nine J = 2 para-H2O lines, either 202-111(Eup/k = 101 K) or 211-202(Eup/k = 137 K). The apparent luminosities of the H2O emission lines are μLH2O 6-21 × 108 L⊙ (3 <μ< 15, where μ is the lens magnification factor), with velocity-integrated line fluxes ranging from 4-15 Jy km s-1. We have also observed CO emission lines using EMIR on the IRAM 30 m telescope in seven sources (most of those have not yet had their CO emission lines observed). The velocity widths for CO and H2O lines are found to be similar, generally within 1σ errors in the same source. With almost comparable integrated flux densities to those of the high-J CO line (ratios range from 0.4 to 1.1), H2O is found to be among the strongest molecular emitters in high-redshift Hy/ULIRGs. We also confirm our previously found correlation between luminosity of H2O (LH2O) and infrared (LIR) that LH2O LIR1.1-1.2, with ournew detections. This correlation could be explained by a dominant role of far-infrared pumping in the H2O excitation. Modelling reveals that the far-infrared radiation fields have warm dust temperature Twarm 45-75 K, H2O column density per unit velocity interval NH2O /ΔV ≳ 0.3 × 1015 cm-2 km-1 s and 100 μm continuum opacity τ100> 1 (optically thick), indicating that H2O is likely to trace highly obscured warm dense gas. However, further observations of J ≥ 4 H2O lines are needed to better constrain the continuum optical depth and other physical conditions of the molecular gas and dust. We have also detected H2O+ emission in three sources. A tight correlation

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar-75%CO2-12%H2O

NASA Astrophysics Data System (ADS)

Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

2013-11-01

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar-75%CO2-12%H2O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe2O3 and spinel was observed after 50 h exposure in the presence of 12% H2O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr2O4, Fe3O4 and Fe2O3 were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr2O3 layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.

Vibrations and reorientations of H2O molecules in [Sr(H2O)6]Cl2 studied by Raman light scattering, incoherent inelastic neutron scattering and proton magnetic resonance.

PubMed

Hetmańczyk, Joanna; Hetmańczyk, Lukasz; Migdał-Mikuli, Anna; Mikuli, Edward; Florek-Wojciechowska, Małgorzata; Harańczyk, Hubert

2014-04-24

Vibrational-reorientational dynamics of H2O ligands in the high- and low-temperature phases of [Sr(H2O)6]Cl2 was investigated by Raman Spectroscopy (RS), proton magnetic resonance ((1)H NMR), quasielastic and inelastic incoherent Neutron Scattering (QENS and IINS) methods. Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS, did not indicated a change of the crystal structure at the phase transition (detected earlier by differential scanning calorimetry (DSC) at TC(h)=252.9 K (on heating) and at TC(c)=226.5K (on cooling)). Temperature dependence of the full-width at half-maximum (FWHM) of νs(OH) band at ca. 3248 cm(-1) in the RS spectra indicated small discontinuity in the vicinity of phase transition temperature, what suggests that the observed phase transition may be associated with a change of the H2O reorientational dynamics. However, an activation energy value (Ea) for the reorientational motions of H2O ligands in both phases is nearly the same and equals to ca. 8 kJ mol(-1). The QENS peaks, registered for low temperature phase do not show any broadening. However, in the high temperature phase a small QENS broadening is clearly visible, what implies that the reorientational dynamics of H2O ligands undergoes a change at the phase transition. (1)H NMR line is a superposition of two powder Pake doublets, differentiated by a dipolar broadening, suggesting that there are two types of the water molecules in the crystal lattice of [Sr(H2O)6]Cl2 which are structurally not equivalent average distances between the interacting protons are: 1.39 and 1.18 Å. However, their reorientational dynamics is very similar (τc=3.3⋅10(-10) s). Activation energies for the reorientational motion of these both kinds of H2O ligands have nearly the same values in an experimental error limit: and equal to ca. 40 kJ mole(-1). The phase transition is not seen in the (1)H NMR spectra temperature dependencies. Infrared (IR), Raman (RS) and inelastic

H2O Paradox and its Implications on H2O in Moon

NASA Astrophysics Data System (ADS)

Zhang, Youxue

2017-04-01

The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

A continuous [15O]H2O production and infusion system for PET imaging

NASA Astrophysics Data System (ADS)

Sajjad, Munawwar; Liow, Jeih-San

1999-06-01

A system for continuous production and infusion of [15O]H2O has been designed for PET cerebral blood flow studies. The injection system consists of a four-port-two-position valve, two Horizon Nxt infusion pumps, and a sterile 50 ml vial. The variation of the production of [15O]H2O was <1%. The variation of activity delivered measured by scanner counts during the steady state period was <2%.

Descent without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds.

PubMed

Loeffler, Mark J; Hudson, Reggie L

2015-06-01

The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NH4+ and SO2 making SO(4)2- by H+ and e- transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

Descent Without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds

NASA Technical Reports Server (NTRS)

Loeffler, Mark Josiah; Hudson, Reggie Lester

2015-01-01

The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NHþ 4 and SO2 making SO2 4 by H+ and e - transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

NASA Technical Reports Server (NTRS)

Rao, D. B.; Jacob, K. T.; Nelson, H. G.

1981-01-01

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.

Characterization of a real time H2O2 monitor for use in studies on H2O2 production by antibodies and cells.

PubMed

Sharma, Harish A; Balcavage, Walter X; Waite, Lee R; Johnson, Mary T; Nindl, Gabi

2003-01-01

It was recently shown that antibodies catalyze a reaction between water and ultraviolet light (UV) creating singlet oxygen and ultimately H2O2. Although the in vivo relevance of these antibody reactions is unclear, it is interesting that among a wide variety of non-antibody proteins tested, the T cell receptor is the only protein with similar capabilities. In clinical settings UV is believed to exert therapeutic effects by eliminating inflammatory epidermal T cells and we hypothesized that UV-triggered H2O2 production is involved in this process. To test the hypothesis we developed tools to study production of H2O2 by T cell receptors with the long-term goal of understanding, and improving, UV phototherapy. Here, we report the development of an inexpensive, real time H2O2 monitoring system having broad applicability. The detector is a Clark oxygen electrode (Pt, Ag/AgCl) modified to detect UV-driven H2O2 production. Modifications include painting the electrode black to minimize UV effects on the Ag/AgCl electrode and the use of hydrophilic, large pore Gelnots electrode membranes. Electrode current was converted to voltage and then amplified and recorded using a digital multimeter coupled to a PC. A reaction vessel with a quartz window was developed to maintain constant temperature while permitting UV irradiation of the samples. The sensitivity and specificity of the system and its use in cell-free and cell-based assays will be presented. In a cellfree system, production of H2O2 by CD3 antibodies was confirmed using our real time H2O2 monitoring method. Additionally we report the finding that splenocytes and Jurkat T cells also produce H2O2 when exposed to UV light.

Upper limits for the rate constant for the reaction Br + H2O2 yields HB2 + HO2

NASA Technical Reports Server (NTRS)

Leu, M.-T.

1980-01-01

Upper limits for the rate constant for the reaction Br + H2O2 yields HBr + HO2 have been measured over the temperature range 298 to 417 K in a discharge flow system using a mass spectrometer as a detector. Results are k sub 1 less than 1.5 x 10 to the -15th power cu cm/s at 298 K and k sub 1 less than 3.0 x 10 to the -15th power cu cm/s at 417 K, respectively. The implication to stratospheric chemistry is discussed.

Single-component and binary CO2 and H2O adsorption of amine-functionalized cellulose.

PubMed

Gebald, Christoph; Wurzbacher, Jan A; Borgschulte, Andreas; Zimmermann, Tanja; Steinfeld, Aldo

2014-02-18

A fundamental analysis of single-component and binary CO2 and H2O adsorption of amine-functionalized nanofibrillated cellulose is carried out in the temperature range of 283-353 K and at CO2 partial pressures in the range of 0.02-105 kPa, where the ultralow partial pressure range is relevant for the direct capture of CO2 from atmospheric air. Single-component CO2 and H2O adsorption experimental data are fitted to the Toth and Guggenheim-Anderson-de Boer models, respectively. Corresponding heats of adsorption, derived from explicit solutions of the van't Hoff equation, are -50 kJ/mol CO2 and -48.8 kJ/mol H2O. Binary CO2/H2O adsorption measurements for humid air reveal that the presence of H2O at 2.55 kPa enhances CO2 adsorption, while the presence of CO2 at 0.045 kPa does not influence H2O adsorption. The energy demand of the temperature-vacuum-swing adsorption/desorption cycle for delivering pure CO2 from air increases significantly with H2O adsorption and indicates the need to reduce the hygroscopicity of the adsorbent.

Arsenite oxidation by H 2O 2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Campanella, Luigi; Millero, Frank J.

1999-09-01

The rates of the oxidation of As( III) with H 2O 2 were measured in NaCl solutions as a function of pH (7.5-10.3), temperature (10-50C) and ionic strength ( I = 0.01-4). The rate of the oxidation of As( III) with H 2O 2 can be described by the general expression: d[As( III)]/ dt = k[As( III)] [H 2O 2] where k (mol/L -1 min -1) can be determined from (σ = ±0.12) log k=5.29+1.41 pH-0.57 I+1.40 I0.5-4898/ T. The effect of pH on the rates indicates that the reaction is due to AsO( OH) 2-+ H2O2k 1→productsAsO2( OH) 2-+ H2O2k 2→products, AsO33-+ H2O2k 3→products where k = k1 α AsO(OH) 2- + k2 α AsO 2(OH) 2- + k3 α AsO 3 3- and α i are the molar fraction of species i. The values of k1 = 42 ± 20, k2 = (8 ± 1) × 10 4, and k3 = (72 ± 18) × 10 6 mol/L -1 min -1 were found at 25C and I = 0.01 mol/L. The undissociated As(OH) 3 does not react with H 2O 2. The effect of ionic strength on the rate constants has been attributed to the effect of ionic strength on the speciation of As( III). The rate expression has been shown to be valid for NaClO 4 solutions, northern Adriatic sea waters, and Tiber River waters. The cations Fe 2+ and Cu 2+ were found to exert a catalytic effect on the rates. Cu 2+ plays a role at concentration levels (>0.1 μmol/L) which are typical of polluted aquatic systems, while Fe 2+ is important at levels which may be found in lacustrine environments (>5-10 μmol/L). The reaction of As( III) with H 2O 2 may play a role in marine and lacustrine surface waters limiting the accumulation of As( III) resulting from biologically mediated reduction processes of As( V).

Effect of atomic layer deposition temperature on current conduction in Al2O3 films formed using H2O oxidant

NASA Astrophysics Data System (ADS)

Hiraiwa, Atsushi; Matsumura, Daisuke; Kawarada, Hiroshi

2016-08-01

To develop high-performance, high-reliability gate insulation and surface passivation technologies for wide-bandgap semiconductor devices, the effect of atomic layer deposition (ALD) temperature on current conduction in Al2O3 films is investigated based on the recently proposed space-charge-controlled field emission model. Leakage current measurement shows that Al2O3 metal-insulator-semiconductor capacitors formed on the Si substrates underperform thermally grown SiO2 capacitors at the same average field. However, using equivalent oxide field as a more practical measure, the Al2O3 capacitors are found to outperform the SiO2 capacitors in the cases where the capacitors are negatively biased and the gate material is adequately selected to reduce virtual dipoles at the gate/Al2O3 interface. The Al2O3 electron affinity increases with the increasing ALD temperature, but the gate-side virtual dipoles are not affected. Therefore, the leakage current of negatively biased Al2O3 capacitors is approximately independent of the ALD temperature because of the compensation of the opposite effects of increased electron affinity and permittivity in Al2O3. By contrast, the substrate-side sheet of charge increases with increasing ALD temperature above 210 °C and hence enhances the current of positively biased Al2O3 capacitors more significantly at high temperatures. Additionally, an anomalous oscillatory shift of the current-voltage characteristics with ALD temperature was observed in positively biased capacitors formed by low-temperature (≤210 °C) ALD. This shift is caused by dipoles at the Al2O3/underlying SiO2 interface. Although they have a minimal positive-bias leakage current, the low-temperature-grown Al2O3 films cause the so-called blisters problem when heated above 400 °C. Therefore, because of the absence of blistering, a 450 °C ALD process is presently the most promising technology for growing high-reliability Al2O3 films.

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

Photodesorption of H2O, HDO, and D2O ice and its impact on fractionation

NASA Astrophysics Data System (ADS)

Arasa, Carina; Koning, Jesper; Kroes, Geert-Jan; Walsh, Catherine; van Dishoeck, Ewine F.

2015-03-01

The HDO/H2O ratio measured in interstellar gas is often used to draw conclusions on the formation and evolution of water in star-forming regions and, by comparison with cometary data, on the origin of water on Earth. In cold cores and in the outer regions of protoplanetary disks, an important source of gas-phase water comes from photodesorption of water ice. This research note presents fitting formulae for implementation in astrochemical models using previously computed photodesorption efficiencies for all water ice isotopologues obtained with classical molecular dynamics simulations. The results are used to investigate to what extent the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during the photodesorption process. Probabilities for the top four monolayers are presented for photodesorption of X (X = H, D) atoms, OX radicals, and X2O and HDO molecules following photodissociation of H2O, D2O, and HDO in H2O amorphous ice at ice temperatures from 10-100 K. Significant isotope effects are found for all possible products: (1) H atom photodesorption probabilities from H2O ice are larger than those for D atom photodesorption from D2O ice by a factor of 1.1; the ratio of H and D photodesorbed upon HDO photodissociation is a factor of 2. This process will enrich the ice in deuterium atoms over time; (2) the OD/OH photodesorption ratio upon D2O and H2O photodissociation is on average a factor of 2, but the OD/OH photodesorption ratio upon HDO photodissociation is almost constant at unity for all ice temperatures; (3) D atoms are more effective in kicking out neighbouring water molecules than H atoms. However, the ratio of the photodesorbed HDO and H2O molecules is equal to the HDO/H2O ratio in the ice, therefore, there is no isotope fractionation when HDO and H2O photodesorb from the ice. Nevertheless, the enrichment of the ice in D atoms due to photodesorption can over time lead to an enhanced HDO/H2O ratio in the ice, and

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

H2O in rhyolitic glasses and melts: Measurement, speciation, solubility, and diffusion

NASA Astrophysics Data System (ADS)

Zhang, Youxue

1999-11-01

Dissolved H2O in silicate melts and glasses plays a crucial role in volcanic eruptions on terrestrial planets and affects glass properties and magma evolution. In this paper, major progress on several aspects of the H2O-melt (or glass) system is reviewed, consistency among a variety of data is investigated, discrepancies are evaluated, and confusion is clarified. On the infrared measurement of total H2O and species concentrations, calibration for a variety of glasses has been carried out at room temperature. The measurements for H2O in rhyolitic glasses have undergone the most scrutiny, resulting in the realization that absorptivities for the near-infrared bands depend on total H2O content. Although the variation of the absorptivities does not seem to significantly affect the determination of total H2O, it does affect the determination of molecular H2O and OH species concentrations. Calibration of the infrared technique for H2O in rhyolitic glasses still needs much improvement, especially at high total H2O. Furthermore, it is now almost certain that the molar absorptivities also depend on the measurement temperature in in situ studies. Hence it will be necessary to carry out calibrations in situ at high temperatures. On H2O speciation, results from two experimental approaches, the quench technique and the in situ technique, are very different, leading to controversy in our understanding of true speciation. A solution is presented to reconcile this controversy. It is almost certain that the quench technique does not suffer from a quench problem, but interpretation of in situ results suffered from ignoring the dependence of the molar absorptivities on measurement temperature. Accurate calibration at high temperatures is necessary for the quantitative application of the in situ technique to H2O speciation in silicate melts and glasses. On H2O solubility in silicate melts, recent experimental work has significantly expanded the T-P range of solubility measurements, and

Low Temperature Synthesized H2Ti3O7 Nanotubes with a High CO2 Adsorption Property by Amine Modification.

PubMed

Ota, Misaki; Hirota, Yuichiro; Uchida, Yoshiaki; Sakamoto, Yasuhiro; Nishiyama, Norikazu

2018-06-12

Carbon dioxide (CO 2 ) capture and storage (CCS) technologies have been attracting attention in terms of tackling with global warming. To date, various CO 2 capture technologies including solvents, membranes, cryogenics, and solid adsorbents have been proposed. Currently, a liquid adsorption method for CO 2 using amine solution (monoethanolamine) has been practically used. However, this liquid phase CO 2 adsorption process requires heat regeneration, and it can cause many problems such as corrosion of equipment and degradation of the solution. Meanwhile, solid adsorption methods using porous materials are more advantageous over the liquid method at these points. In this context, we here evaluated if hydrogen titanate (H 2 Ti 3 O 7 ) nanotubes and the surface modification effectively capture CO 2 . For this aim, we first developed a facile synthesis method of H 2 Ti 3 O 7 nanotubes different from any conventional methods. Briefly, they were converted from the precursors-amorphous TiO 2 nanoparticles at room temperature (25 °C). We then determined the outer and the inner diameters of the H 2 Ti 3 O 7 nanotubes as 3.0 and 0.7 nm, respectively. It revealed that both values were much smaller than the reported ones; thus the specific surface area showed the highest value (735 m 2 /g). Next, the outer surface of H 2 Ti 3 O 7 nanotubes was modified using ethylenediamine to examine if CO 2 adsorption capacity increases. The ethylendiamine-modified H 2 Ti 3 O 7 nanotubes showed a higher CO 2 adsorption capacity (50 cm 3 /g at 0 °C, 100 kPa). We finally concluded that the higher CO 2 adsorption capacity could be explained, not only by the high specific surface area of the nanotubes but also by tripartite hydrogen bonding interactions among amines, CO 2 , and OH groups on the surface of H 2 Ti 3 O 7 .

Low-temperature atomic layer deposition of SiO2/Al2O3 multilayer structures constructed on self-standing films of cellulose nanofibrils

NASA Astrophysics Data System (ADS)

Putkonen, Matti; Sippola, Perttu; Svärd, Laura; Sajavaara, Timo; Vartiainen, Jari; Buchanan, Iain; Forsström, Ulla; Simell, Pekka; Tammelin, Tekla

2017-12-01

In this paper, we have optimized a low-temperature atomic layer deposition (ALD) of SiO2 using AP-LTO® 330 and ozone (O3) as precursors, and demonstrated its suitability to surface-modify temperature-sensitive bio-based films of cellulose nanofibrils (CNFs). The lowest temperature for the thermal ALD process was 80°C when the silicon precursor residence time was increased by the stop-flow mode. The SiO2 film deposition rate was dependent on the temperature varying within 1.5-2.2 Å cycle-1 in the temperature range of 80-350°C, respectively. The low-temperature SiO2 process that resulted was combined with the conventional trimethyl aluminium + H2O process in order to prepare thin multilayer nanolaminates on self-standing CNF films. One to six stacks of SiO2/Al2O3 were deposited on the CNF films, with individual layer thicknesses of 3.7 nm and 2.6 nm, respectively, combined with a 5 nm protective SiO2 layer as the top layer. The performance of the multilayer hybrid nanolaminate structures was evaluated with respect to the oxygen and water vapour transmission rates. Six stacks of SiO2/Al2O with a total thickness of approximately 35 nm efficiently prevented oxygen and water molecules from interacting with the CNF film. The oxygen transmission rates analysed at 80% RH decreased from the value for plain CNF film of 130 ml m-2 d-1 to 0.15 ml m-2 d-1, whereas the water transmission rates lowered from 630 ± 50 g m-2 d-1 down to 90 ± 40 g m-2 d-1. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.