Recent decreases in fossil-fuel emissions of ethane and methane derived from firn air.

Science.gov (United States)

Aydin, Murat; Verhulst, Kristal R; Saltzman, Eric S; Battle, Mark O; Montzka, Stephen A; Blake, Donald R; Tang, Qi; Prather, Michael J

2011-08-10

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20 years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1 Tg = 10(12) g) and dropped to 8-10 Tg  yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.

Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

Science.gov (United States)

Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

2010-09-09

Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

Distribution and origin of dissolved methane, ethane and propane in shallow groundwater of Lower Saxony, Germany

International Nuclear Information System (INIS)

Schloemer, S.; Elbracht, J.; Blumenberg, M.; Illing, C.J.

2016-01-01

More than 90% of Germany's domestic natural gas production and reserves are located in Lower Saxony, North Germany. Recently, research has been intensified with respect to unconventional shale gas, revealing a large additional resource potential in northern Germany. However, many concerns arise within the general public and government/political institutions over potential groundwater contamination from additional gas wells through hydraulic fracturing operations. In order to determine the naturally occurring background methane concentrations, ∼1000 groundwater wells, covering ∼48 000 km 2 , have been sampled and subsequently analyzed for dissolved methane, ethane and propane and the isotopic composition of methane (δ 13 C). Dissolved methane concentrations cover a range of ∼7 orders of magnitude between the limit of quantification at ∼20 nl/l and 60 ml/l. The majority of groundwater wells exhibit low concentrations (<1 μl/l), a small number of samples (65) reveal concentration in the range >10 ml/l. In 27% of all samples ethane and in 8% ethane and propane was detected. The median concentration of both components is generally very low (ethane 50 nl/l, propane 23 nl/l). Concentrations reveal a bimodal distribution of the dissolved gas, which might mirror a regional trend due to different hydrogeological settings. The isotopic composition of methane is normally distributed (mean ∼ −70‰ vs PDB), but shows a large variation between −110‰ and +20‰. Samples with δ 13 C values lower than −55‰ vs PDB (66%) are indicative for methanogenic biogenic processes. 5% of the samples are unusually enriched in 13 C (≥25‰ vs PDB) and can best be explained by microbial methane oxidation. According to a standard diagnostic diagram based on methane δ 13 C values and the ratio of methane over the sum over ethane plus propane (“Bernard”-diagram) less than 4% of the samples plot into the diagnostic field of typical thermogenic natural

Fugitive Methane Emission Identification and Source Attribution: Ethane-to-Methane Analysis Using a Portable Cavity Ring-Down Spectroscopy Analyzer

Science.gov (United States)

Kim-Hak, D.; Fleck, D.

2017-12-01

Natural gas analysis and methane specifically have become increasingly important by virtue of methane's 28-36x greenhouse warming potential compared to CO2 and accounting for 10% of total greenhouse gas emissions in the US alone. Additionally, large uncontrolled leaks, such as the recent one from Aliso Canyon in Southern California, originating from uncapped wells, storage facilities and coal mines have increased the total global contribution of methane missions even further. Determining the specific fingerprint of methane sources by quantifying the ethane to methane (C2:C1) ratios provides us with means to understand processes yielding methane and allows for sources of methane to be mapped and classified through these processes; i.e. biogenic or thermogenic, oil vs. gas vs. coal gas-related. Here we present data obtained using a portable cavity ring-down spectrometry analyzer weighing less than 25 lbs and consuming less than 35W that simultaneously measures methane and ethane in real-time with a raw 1-σ precision of plane gas propagation.

Methane, Black Carbon, and Ethane Emissions from Natural Gas Flares in the Bakken Shale, North Dakota.

Science.gov (United States)

Gvakharia, Alexander; Kort, Eric A; Brandt, Adam; Peischl, Jeff; Ryerson, Thomas B; Schwarz, Joshua P; Smith, Mackenzie L; Sweeney, Colm

2017-05-02

Incomplete combustion during flaring can lead to production of black carbon (BC) and loss of methane and other pollutants to the atmosphere, impacting climate and air quality. However, few studies have measured flare efficiency in a real-world setting. We use airborne data of plume samples from 37 unique flares in the Bakken region of North Dakota in May 2014 to calculate emission factors for BC, methane, ethane, and combustion efficiency for methane and ethane. We find no clear relationship between emission factors and aircraft-level wind speed or between methane and BC emission factors. Observed median combustion efficiencies for methane and ethane are close to expected values for typical flares according to the US EPA (98%). However, we find that the efficiency distribution is skewed, exhibiting log-normal behavior. This suggests incomplete combustion from flares contributes almost 1/5 of the total field emissions of methane and ethane measured in the Bakken shale, more than double the expected value if 98% efficiency was representative. BC emission factors also have a skewed distribution, but we find lower emission values than previous studies. The direct observation for the first time of a heavy-tail emissions distribution from flares suggests the need to consider skewed distributions when assessing flare impacts globally.

Potential for cometabolic biodegradation of 1,4-dioxane in aquifers with methane or ethane as primary substrates.

Science.gov (United States)

Hatzinger, Paul B; Banerjee, Rahul; Rezes, Rachael; Streger, Sheryl H; McClay, Kevin; Schaefer, Charles E

2017-12-01

The objective of this research was to evaluate the potential for two gases, methane and ethane, to stimulate the biological degradation of 1,4-dioxane (1,4-D) in groundwater aquifers via aerobic cometabolism. Experiments with aquifer microcosms, enrichment cultures from aquifers, mesophilic pure cultures, and purified enzyme (soluble methane monooxygenase; sMMO) were conducted. During an aquifer microcosm study, ethane was observed to stimulate the aerobic biodegradation of 1,4-D. An ethane-oxidizing enrichment culture from these samples, and a pure culture capable of growing on ethane (Mycobacterium sphagni ENV482) that was isolated from a different aquifer also biodegraded 1,4-D. Unlike ethane, methane was not observed to appreciably stimulate the biodegradation of 1,4-D in aquifer microcosms or in methane-oxidizing mixed cultures enriched from two different aquifers. Three different pure cultures of mesophilic methanotrophs also did not degrade 1,4-D, although each rapidly oxidized 1,1,2-trichloroethene (TCE). Subsequent studies showed that 1,4-D is not a substrate for purified sMMO enzyme from Methylosinus trichosporium OB3b, at least not at the concentrations evaluated, which significantly exceeded those typically observed at contaminated sites. Thus, our data indicate that ethane, which is a common daughter product of the biotic or abiotic reductive dechlorination of chlorinated ethanes and ethenes, may serve as a substrate to enhance 1,4-D degradation in aquifers, particularly in zones where these products mix with aerobic groundwater. It may also be possible to stimulate 1,4-D biodegradation in an aerobic aquifer through addition of ethane gas. Conversely, our results suggest that methane may have limited importance in natural attenuation or for enhancing biodegradation of 1,4-D in groundwater environments.

How to get relations between bedrocks and δ13C values of methane and ethane in natural gases?

International Nuclear Information System (INIS)

Schuetze, H.; Muehle, K.

1987-01-01

Basing on the hypothesis that δ 13 C values of different carbon positions within biomolecules are thermodynamically controlled a model was derived to evaluate δ 13 C values of methane and ethane in the process of thermal genesis from organic matter in bedrocks. To get information about genesis and postgenetic history of a certain natural gas it is necessary to measure both, δ 13 C of methane (C 1 ) and of ethane (C 2 ), too. The isotopic composition of ethane will be nearly unchanged after genesis. In contrast to this the isotopic composition of methane can be changed drastically by molecular diffusion. Therefore δ 13 C of ethane is a well defined indicator of the genesis conditions. (author)

Dissociation heat of mixed-gas hydrate composed of methane and ethane

Energy Technology Data Exchange (ETDEWEB)

Hachikubo, A.; Nakagawa, R.; Kubota, D.; Sakagami, H.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan)

2008-07-01

Formation and dissociation processes of natural gas hydrates in permafrost, marine and lake sediments are highly controlled by their thermal properties. Dissociation heat of gas hydrates can be estimated from phase equilibrium data using the Clausius-Clapeyron equation. However, this method is applicable for pure gas hydrate and at a temperature of 0 degrees Celsius. Direct calorimetric measurements on gas hydrates using a calorimeter have been developed to obtain thermal properties of gas hydrates, including dissociation heat and heat capacity. Studies have shown that a structure 2 gas hydrate appears in appropriate gas composition of methane and ethane. This paper investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. Raman spectroscopy was used to confirm the appearance of a structure 2 gas hydrate. The paper identified the experimental procedure and discussed sample preparation, Raman spectroscopy, and calorimetric measurements. A schematic diagram of the calorimeter was also presented. It was concluded that in most cases, two stages of dissociation were found at the dissociation process. 15 refs., 6 figs.

Observation of ice sheet formation on methane and ethane gas hydrates using a scanning confocal microscopy

Energy Technology Data Exchange (ETDEWEB)

Nagao, J.; Shimomura, N.; Ebinuma, T.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira, Sapporo (Japan). Methane Hydrate Research Lab.

2008-07-01

Interest in gas hydrates has increased in recent years due to the discovery of large deposits under the ocean floor and in permafrost regions. Natural gas hydrates, including methane, is expected to become a new energy source and a medium for energy storage and transportation. Gas hydrates consist of an open network of water molecules that are hydrogen-bonded in a similar manner to ice. Gas molecules are interstitially engaged under high pressures and low temperatures. Although the dissociation temperature of methane hydrate under atmospheric pressure is about 193 K, studies have shown that methane hydrate can be stored at atmospheric pressure and 267 K for 2 years. Because of this phenomenon, known as self-preservation, transportation and storage of methane hydrate can occur at temperature conditions milder than those for liquefied methane gas at atmospheric pressure. This study examined the surface changes of methane and ethane hydrates during dissociation using an optical microscope and confocal scanning microscope (CSM). This paper reported on the results when the atmospheric gas pressure was decreased. Ice sheets formed on the surfaces of methane and ethane gas hydrates due to depressurizing dissociation of methane and ethane hydrates when the methane and ethane gas pressures were decreased at designated temperatures. The dissociation of methane gas hydrate below below 237 K resulted in the generation of small ice particles on the hydrate surface. A transparent ice sheet formed on the hydrate surface above 242 K. The thickness of the ice sheet on the methane hydrate surface showed the maximum of ca. 30 {mu}m at 253 K. In the case of ethane hydrates, ice particles and ice sheets formed below 262 and 267 respectively. Since the ice particles and ice sheets were formed by water molecules generated during the gas hydrate dissociation, the mechanism of ice sheet formation depends on the dissociation rate of hydrate, ice particle sintering rate, and water molecule

Gamma-radiolysis of the 2-methyl-2-propanol-water system: yields of methane and ethane

International Nuclear Information System (INIS)

Silaev, M.M.; Afanas'ev, A.M.; Kalyazin, E.P.

1991-01-01

The dependence of methane and ethane yields on the concentration and corresponding electron part of alcohol during γ-radiolysis of 2-methyl-2-propanol-water system has been investigated. Irradiation was realized at room temperature, dose rate of 7.7 Gy/s up to absorbed doses of 0.4-14 kGy. The observed deviations of radiation-chemical yields of products from additivity rule, positive in case of methane and negative in case of ethane, are explained

Methane source identification in Boston, Massachusetts using isotopic and ethane measurements

Science.gov (United States)

Down, A.; Jackson, R. B.; Plata, D.; McKain, K.; Wofsy, S. C.; Rella, C.; Crosson, E.; Phillips, N. G.

2012-12-01

Methane has substantial greenhouse warming potential and is the principle component of natural gas. Fugitive natural gas emissions could be a significant source of methane to the atmosphere. However, the cumulative magnitude of natural gas leaks is not yet well constrained. We used a combination of point source measurements and ambient monitoring to characterize the methane sources in the Boston urban area. We developed distinct fingerprints for natural gas and multiple biogenic methane sources based on hydrocarbon concentration and isotopic composition. We combine these data with periodic measurements of atmospheric methane and ethane concentration to estimate the fractional contribution of natural gas and biogenic methane sources to the cumulative urban methane flux in Boston. These results are used to inform an inverse model of urban methane concentration and emissions.

Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

Science.gov (United States)

Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

2009-01-01

We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

AIRBORNE, OPTICAL REMOTE SENSNG OF METHANE AND ETHANE FOR NATURAL GAS PIPELINE LEAK DETECTION

Energy Technology Data Exchange (ETDEWEB)

Jerry Myers

2005-04-15

Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. The scope of the work involved designing and developing an airborne, optical remote sensor capable of sensing methane and, if possible, ethane for the detection of natural gas pipeline leaks. Flight testing using a custom dual wavelength, high power fiber amplifier was initiated in February 2005. Ophir successfully demonstrated the airborne system, showing that it was capable of discerning small amounts of methane from a simulated pipeline leak. Leak rates as low as 150 standard cubic feet per hour (scf/h) were detected by the airborne sensor.

Molecular dynamics study on the structure I clathrate-hydrate of methane + ethane mixture

International Nuclear Information System (INIS)

Erfan-Niya, Hamid; Modarress, Hamid; Zaminpayma, Esmaeil

2011-01-01

Molecular dynamics (MD) simulations are used to study the structure I stability of methane + ethane clathrate-hydrates at temperatures 273, 275 and 277 K. NVT- and NPT-ensembles are utilized in MD simulation, and each consists of 3 x 3 x 3 replica unit cells containing 46 water molecules which are considered as the host molecules and up to eight methane + ethane molecules considered as the guest molecules. In MD simulations for host-host interactions, the potential model used was a type of simple point charge (SPC) model, and for guest-guest and host-guest interactions the potential used was Lennard-Jones model. In the process of MD simulation, achieving equilibrium of the studied system was recognized by stability in calculated pressure for NVT-ensemble and volume for NPT-ensemble. To understand the characteristic configurations of the structure I hydrate, the radial distribution functions (RDFs) of host-host, host-guest and guest-guest molecules as well as other properties including kinetic energy, potential energy and total energy were calculated. The results show that guest molecules interaction with host molecules cannot decompose the hydrate structure, and these results are consistent with most previous experimental and theoretical investigations that methane + ethane mixtures form structure I hydrates over the entire mixture composition range.

The Global Search for Abiogenic GHGs, via Methane Isotopes and Ethane

Science.gov (United States)

Malina, Edward; Muller, Jan-Peter; Walton, David; Potts, Dale

2015-04-01

The importance of Methane as an anthropogenic Green House Gas (GHG) is well recognized in the scientific community, and is second only to Carbon Dioxide in terms of influence on the Earth's radiation budget (Parker, et al, 2011) suggesting that the ability to apportion the source of the methane (whether it is biogenic, abiogenic or thermogenic) has never been more important. It has been proposed (Etiope, 2009) that it may be possible to distinguish between a biogenic methane source (e.g. bacteria fermentation) and an abiogenic source (e.g. gas seepage or fugitive emissions) via the retrieval of the abundances of methane isotopes (12CH4 and 13CH4) and through the ratio of ethane (C2H6) to methane (CH4) concentrations. Using ultra fine spectroscopy (simulations, we show that it is possible to distinguish between methane isotopes using the FTS based instruments on ACE and GOSAT, and retrieve the abundances in the Short Wave Infra-red (SWIR) at 1.65μm, 2.3μm, 3.3μm and Thermal IR, 7.8μm wavebands for methane, and the 3.3μm and 7μm wavebands for ethane. Initially we use the spectral line database HITRAN to determine the most appropriate spectral waveband to retrieve methane isotopes (and ethane) with minimal water vapour, CO2 and NO2 impact. Following this, we have evaluated the detectability of these trace gases using the more sophisticated Radiative Transfer Models (RTMs) SCIATRAN, the Oxford RFM and MODTRAN 5 in the SWIR, in order to determine the barriers to retrieving methane isotopes in both ACE (limb profile) and GOSAT (nadir measurements) instruments, including a preliminary investigation into the effects of clouds, aerosols, surface reflectance on the retrieval of methane isotopes. The aim of these RTM simulations is to further narrow down the spectral regions (originally identified in the HITRAN assessment) where methane isotopes can/may be retrieved from orbit. The key outputs from the RTM study are absorption and radiance data, which allow us to

Natural gas fugitive emissions rates constrained by global atmospheric methane and ethane.

Science.gov (United States)

Schwietzke, Stefan; Griffin, W Michael; Matthews, H Scott; Bruhwiler, Lori M P

2014-07-15

The amount of methane emissions released by the natural gas (NG) industry is a critical and uncertain value for various industry and policy decisions, such as for determining the climate implications of using NG over coal. Previous studies have estimated fugitive emissions rates (FER)--the fraction of produced NG (mainly methane and ethane) escaped to the atmosphere--between 1 and 9%. Most of these studies rely on few and outdated measurements, and some may represent only temporal/regional NG industry snapshots. This study estimates NG industry representative FER using global atmospheric methane and ethane measurements over three decades, and literature ranges of (i) tracer gas atmospheric lifetimes, (ii) non-NG source estimates, and (iii) fossil fuel fugitive gas hydrocarbon compositions. The modeling suggests an upper bound global average FER of 5% during 2006-2011, and a most likely FER of 2-4% since 2000, trending downward. These results do not account for highly uncertain natural hydrocarbon seepage, which could lower the FER. Further emissions reductions by the NG industry may be needed to ensure climate benefits over coal during the next few decades.

Identification of novel methane-, ethane-, and propane-oxidizing bacteria at marine hydrocarbon seeps by stable isotope probing.

Science.gov (United States)

Redmond, Molly C; Valentine, David L; Sessions, Alex L

2010-10-01

Marine hydrocarbon seeps supply oil and gas to microorganisms in sediments and overlying water. We used stable isotope probing (SIP) to identify aerobic bacteria oxidizing gaseous hydrocarbons in surface sediment from the Coal Oil Point seep field located offshore of Santa Barbara, California. After incubating sediment with (13)C-labeled methane, ethane, or propane, we confirmed the incorporation of (13)C into fatty acids and DNA. Terminal restriction fragment length polymorphism (T-RFLP) analysis and sequencing of the 16S rRNA and particulate methane monooxygenase (pmoA) genes in (13)C-DNA revealed groups of microbes not previously thought to contribute to methane, ethane, or propane oxidation. First, (13)C methane was primarily assimilated by Gammaproteobacteria species from the family Methylococcaceae, Gammaproteobacteria related to Methylophaga, and Betaproteobacteria from the family Methylophilaceae. Species of the latter two genera have not been previously shown to oxidize methane and may have been cross-feeding on methanol, but species of both genera were heavily labeled after just 3 days. pmoA sequences were affiliated with species of Methylococcaceae, but most were not closely related to cultured methanotrophs. Second, (13)C ethane was consumed by members of a novel group of Methylococcaceae. Growth with ethane as the major carbon source has not previously been observed in members of the Methylococcaceae; a highly divergent pmoA-like gene detected in the (13)C-labeled DNA may encode an ethane monooxygenase. Third, (13)C propane was consumed by members of a group of unclassified Gammaproteobacteria species not previously linked to propane oxidation. This study identifies several bacterial lineages as participants in the oxidation of gaseous hydrocarbons in marine seeps and supports the idea of an alternate function for some pmoA-like genes.

Methane, Ethane, and Propane Sensor for Real-time Leak Detection and Diagnostics

Energy Technology Data Exchange (ETDEWEB)

Roscioli, Joseph R. [Aerodyne Research, Inc., Billerica, MA (United States); Herndon, Scott [Aerodyne Research, Inc., Billerica, MA (United States); Nelson, David D. [Aerodyne Research, Inc., Billerica, MA (United States); Yacovitch, Tara [Aerodyne Research, Inc., Billerica, MA (United States)

2017-03-24

The Phase I effort demonstrated the technical viability of a fast, sensitive, mobile hydrocarbon monitor. The instrument will enable the oil and gas industry, researchers, and regulators to rapidly identify and chemically profile leaks from facilities. This capability will allow operators to quickly narrow down and mitigate probable leaking equipment, minimizing product loss and penalties due to regulatory non-compliance. During the initial development phase, we demonstrated operation of a prototype monitor that is capable of measuring methane, ethane, and propane at sub-part-per-billion sensitivities in 1 second, using direct absorption infrared spectroscopy. To our knowledge, this is the first instrument capable of fast propane measurements at atmospheric concentrations. In addition, the electrical requirements of the monitor have been reduced from the 1,200 W typical of a spectrometer, to <500 W, making it capable of being powered by a passenger vehicle, and easily deployed by the industry. The prototype monitor leverages recent advances in laser technology, using high-efficiency interband cascade lasers to access the 3 μm region of the mid-infrared, where the methane, ethane, and propane absorptions are strongest. Combined with established spectrometer technology, we have achieved precisions below 200 ppt for each compound. This allows the monitor to measure fast plumes from oil and gas facilities, as well as ambient background concentrations (typical ambient levels are 2 ppm, 1.5 ppb, and 0.7 ppb for methane, ethane and propane, respectively). Increases in instrument operating pressure were studied in order to allow for a smaller 125 W pump to be used, and passive cooling was explored to reduce the cooling load by almost 90% relative to active (refrigerated) cooling. In addition, the simulated infrared absorption profiles of ethane and propane were modified to minimize crosstalk between species, achieving <1% crosstalk between ethane and propane. Finally, a

Absorption cross-section measurements of methane, ethane, ethylene and methanol at high temperatures

KAUST Repository

Alrefae, Majed; Es-sebbar, Et-touhami; Farooq, Aamir

2014-01-01

Mid-IR absorption cross-sections are measured for methane, ethane, ethylene and methanol over 2800-3400 cm-1 (2.9-3.6 μm) spectral region. Measurements are carried out using a Fourier-Transform-Infrared (FTIR) spectrometer with temperatures ranging

Selective oxidation of methane to ethane and ethylene over various oxide catalysts

NARCIS (Netherlands)

Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.

1987-01-01

Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

Identification of Novel Methane-, Ethane-, and Propane-Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing ▿ †

Science.gov (United States)

Redmond, Molly C.; Valentine, David L.; Sessions, Alex L.

2010-01-01

Marine hydrocarbon seeps supply oil and gas to microorganisms in sediments and overlying water. We used stable isotope probing (SIP) to identify aerobic bacteria oxidizing gaseous hydrocarbons in surface sediment from the Coal Oil Point seep field located offshore of Santa Barbara, California. After incubating sediment with 13C-labeled methane, ethane, or propane, we confirmed the incorporation of 13C into fatty acids and DNA. Terminal restriction fragment length polymorphism (T-RFLP) analysis and sequencing of the 16S rRNA and particulate methane monooxygenase (pmoA) genes in 13C-DNA revealed groups of microbes not previously thought to contribute to methane, ethane, or propane oxidation. First, 13C methane was primarily assimilated by Gammaproteobacteria species from the family Methylococcaceae, Gammaproteobacteria related to Methylophaga, and Betaproteobacteria from the family Methylophilaceae. Species of the latter two genera have not been previously shown to oxidize methane and may have been cross-feeding on methanol, but species of both genera were heavily labeled after just 3 days. pmoA sequences were affiliated with species of Methylococcaceae, but most were not closely related to cultured methanotrophs. Second, 13C ethane was consumed by members of a novel group of Methylococcaceae. Growth with ethane as the major carbon source has not previously been observed in members of the Methylococcaceae; a highly divergent pmoA-like gene detected in the 13C-labeled DNA may encode an ethane monooxygenase. Third, 13C propane was consumed by members of a group of unclassified Gammaproteobacteria species not previously linked to propane oxidation. This study identifies several bacterial lineages as participants in the oxidation of gaseous hydrocarbons in marine seeps and supports the idea of an alternate function for some pmoA-like genes. PMID:20675448

Photofragmentation spectra of halogenated methanes in the VUV photon energy range

Energy Technology Data Exchange (ETDEWEB)

Cartoni, Antonella, E-mail: antonella.cartoni@uniroma1.it [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185 (Italy); Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo [CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015 (Italy)

2014-05-14

In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

Mobile Measurement of Methane and Ethane for the Detection and Attribution of Natural Gas Pipeline Leaks Using Off-Axis Integrated Output Spectroscopy

Science.gov (United States)

Leen, J. B.; Spillane, S.; Gardner, A.; Hansen, P. C.; Gupta, M.; Baer, D. S.

2015-12-01

Natural gas leaks pose a risk to public safety both because of potential explosions as well as from the greenhouse gas potential of fugitive methane. The rapid and cost effective detection of leaks in natural gas distribution is critical to providing a system that is safe for the public and the environment. Detection of methane from a mobile platform (vehicles, aircraft, etc.) is an accepted method of identifying leaks. A robust approach to differentiating pipeline gas (thermogenic) from other biogenic sources is the detection of ethane along with methane. Ethane is present in nearly all thermogenic gas but not in biogenic sources and its presence can be used to positively identify a gas sample. We present a mobile system for the simultaneous measurement of methane and ethane that is capable of detecting pipeline leaks and differentiating pipeline gas from other biogenic sources such as landfills, swamps, sewers, and enteric fermentation. The mobile system consists of a high precision GPS, sonic anemometer, and methane/ethane analyzer based on off-axis integrated cavity output spectroscopy (OA-ICOS). In order to minimize the system cost and facilitate the wide use of mobile leak detection, the analyzer operates in the near-infrared portion of the spectrum where lasers and optics are significantly less costly than in the mid-infrared. The analyzer is capable of detecting methane with a precision of detecting ethane with a precision of detection of leaks at speeds up to 50 mph. The sonic anemometer, GPS and analyzer inlet are mounted to a generic roof rack for attachment to available fleet vehicles. The system can detect leaks having a downwind concentration of as little as 10 ppb of methane above ambient, while leaks 500 ppb above ambient can be identified as thermogenic with greater than 99% certainty (for gas with 6% ethane). Finally, analysis of wind data provides an estimate of leak direction and distance. The system presented provides a robust, cost effective

Effect of gravity on density distributions and orthopositronium annihilation rates in ethane and methane near the critical point

International Nuclear Information System (INIS)

Sharma, S.C.; Kafle, S.R.S.

1983-01-01

The effect of gravity on density distributions has been studied in ethane and methane near their critical points using the linear-model parametric equation of state. The results obtained from this study are used to further understand the sensitivity of orthopositronium annihilation rates to density fluctuations in molecular gases. It is shown that the influence of gravity is too small to account for the recently observed dependence of orthopositronium annihilation rates on the density of ethane gas at 306.4 K. However, a significant variation in local density vs height is calculated at temperatures closer to the gas--liquid critical point. The density and temperature dependencies of the annihilation rates of orthopositronium atoms, recently observed in ethane and methane gases, are discussed in terms of the findings of this study

Homogeneous nucleation in supersaturated vapors of methane, ethane, and carbon dioxide predicted by brute force molecular dynamics.

Science.gov (United States)

Horsch, Martin; Vrabec, Jadran; Bernreuther, Martin; Grottel, Sebastian; Reina, Guido; Wix, Andrea; Schaber, Karlheinz; Hasse, Hans

2008-04-28

Molecular dynamics (MD) simulation is applied to the condensation process of supersaturated vapors of methane, ethane, and carbon dioxide. Simulations of systems with up to a 10(6) particles were conducted with a massively parallel MD program. This leads to reliable statistics and makes nucleation rates down to the order of 10(30) m(-3) s(-1) accessible to the direct simulation approach. Simulation results are compared to the classical nucleation theory (CNT) as well as the modification of Laaksonen, Ford, and Kulmala (LFK) which introduces a size dependence of the specific surface energy. CNT describes the nucleation of ethane and carbon dioxide excellently over the entire studied temperature range, whereas LFK provides a better approach to methane at low temperatures.

Photoabsorption cross sections of methane and ethane, 1380-1600 A, at T=295 K and T=200 K

International Nuclear Information System (INIS)

Mount, G.H.; Moos, H.W.

1978-01-01

Photoabsorption cross sections of methane and ethane gas have been determined from 1380-1600 A at room and dry-ice temperatures. A small decrease in cross section was measured near the molecular absorption edge for each gas. In addition, the photoabsorption cross sections of ethane at room temperature are found to be in agreement with the measurements of Okabe and Becker rather than more recently determined values

The formation of nitrogeneous compounds in the γ-radiolyses of liquid nitrogen solutions of hydrogen, methane, and ethane

International Nuclear Information System (INIS)

Horigome, Keiichi; Hirokami, Shun-ichi; Sato, Shin

1978-01-01

The γ-radiolyses of liquid nitrogen solutions of hydrogen, methane, and ethane have been reinvestigated. A complete survey of nitrogen-containing products has been attempted. The nitrogeneous compounds observed were ammonia (0.7) and hydrogen azide (0.02) in the case of hydrogen, ammonia (0.3), hydrogen cyanide (0.1), methyl azide (0.01), and a polymer in the case of methane, and ammonia (0.3), hydrogen cyanide (0.05), acetonitrile (0.04), ethyl azide (0.01), and a polymer in the case of ethane. The values in parentheses are the G-values obtained at optimum conditions. The hydrolysis of the polymer obtained with methane gave formaldehyde in amounts which correspond to the fact that the G-value of the nitrogen atoms which were converted into the polymer is about 1.0. In order to explain these results, possible reaction mechanisms are discussed. (auth.)

Electron impact spectra of methane, ethane, and neopentane

International Nuclear Information System (INIS)

Johnson, K.E.; Kim, K.; Johnston, D.B.; Lipsky, S.

1979-01-01

Electron impact spectra of methane, ethane, and neopentane have been obtained at scattering angles of 0 0 and 90 0 and at impact energies from approx. =30 to 250 eV. The data are consistent with the lowest excitation in all of these systems to involve promotion of an electron to a 3s Rydberg-like orbital. Differences between 0 0 and 90 0 onsets are attributed to large-angle intensity enhancements of transitions to the 3s Rydberg triplets. At 90 0 all of the spectra exhibit very similar intensity redistributions with strong enhancement of transitions in the 12 and 15 eV region as compared to lower-lying transitions. Assignments of the spectra and possible origins of the angular dependence are discussed

ANALYSIS OF DISSOLVED METHANE, ETHANE, AND ETHYLENE IN GROUND WATER BY A STANDARD GAS CHROMATOGRAPHIC TECHNIQUE

Science.gov (United States)

The measurement of dissolved gases such as methane, ethane, and ethylene in ground water is important in determining whether intrinsic bioremediation is occurring in a fuel- or solvent-contaminated aquifer. A simple procedure is described for the collection and subsequent analys...

Absorption cross-section measurements of methane, ethane, ethylene and methanol at high temperatures

KAUST Repository

Alrefae, Majed

2014-09-01

Mid-IR absorption cross-sections are measured for methane, ethane, ethylene and methanol over 2800-3400 cm-1 (2.9-3.6 μm) spectral region. Measurements are carried out using a Fourier-Transform-Infrared (FTIR) spectrometer with temperatures ranging 296-1100 K and pressures near atmospheric. As temperature increases, the peak cross-sections decrease but the wings of the bands increase as higher rotational lines appear. Integrated band intensity is also calculated over the measured spectral region and is found to be a very weak function of temperature. The absorption cross-sections of the relatively small fuels studied here show dependence on the bath gas. This effect is investigated by studying the variation of absorption cross-sections at 3.392 μm using a HeNe laser in mixtures of fuel and nitrogen, argon, or helium. Mixtures of fuel with He have the highest value of absorption cross-sections followed by Ar and N2. Molecules with narrow absorption lines, such as methane and methanol, show strong dependence on bath gas than molecules with relatively broader absorption features i.e. ethane and ethylene. © 2014 Elsevier Inc. All rights reserved.

Numerical Study of Contaminant Effects on Combustion of Hydrogen, Ethane, and Methane in Air

Science.gov (United States)

Lai, H. T.; Thomas, S. R.

1995-01-01

A numerical study was performed to assess the effects of vitiated air on the chemical kinetics of hydrogen, ethane, and methane combustion with air. A series of calculations in static reacting systems was performed, where the initial temperature was specified and reactions occurred at constant pressure. Three different types of test flow contaminants were considered: NP, H2O, and a combustion of H2O and CO2. These contaminants are present in the test flows of facilities used for hypersonic propulsion testing. The results were computed using a detailed reaction mechanism and are presented in terms of ignition and reaction times. Calculations were made for a wide range of contaminant concentrations, temperatures and pressures. The results indicate a pronounced kinetic effect over a range of temperatures, especially with NO contamination and, to a lesser degree, with H2O contamination. In all cases studied, CO2 remained kinetically inert, but had a thermodynamic effect on results by acting as a third body. The largest effect is observed with combustion using hydrogen fuel, less effect is seen with combustion of ethane, and little effect of contaminants is shown with methane combustion.

Microbial Formation of Ethane in Anoxic Estuarine Sediments

OpenAIRE

Oremland, Ronald S.

1981-01-01

Estuarine sediment slurries produced methane and traces of ethane when incubated under hydrogen. Formation of methane occurred over a broad temperature range with an optimum above 65°C. Ethane formation had a temperature optimum at 40°C. Formation of these two gases was inhibited by air, autoclaving, incubation at 4 and 80°C, and by the methanogenic inhibitor, 2-bromoethanesulfonic acid. Ethane production was stimulated by addition of ethylthioethanesulfonic acid, and production from ethylthi...

Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

Science.gov (United States)

Lomond, Jasmine S; Tong, Anthony Z

2011-01-01

Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

Cloudy with a Chance of Ice: The Stratification of Titan's Vernal Ponds and Formation of Ethane Ice

Science.gov (United States)

Soderblom, J. M.; Steckloff, J. K.

2017-12-01

Cassini ISS observations revealed regions on Saturn's moon Titan that become significantly darker (lower albedo) following storm events [1]. These regions are observed to be topographically low [2], indicating that liquid (predominantly methane-ethane-nitrogen) is pooling on Titan after these storm events. These dark ponds, however, are then observed to significantly brighten (higher albedo relative to pre-storm albedo), before fading to their pre-storm albedos [2-3]. We interpret these data to indicate ethane ice formation, which cools from evaporation of methane. The formation of ethane ices results from a unique sequence of thermophysical and thermochemical phenomena. Initially, the methane in the mixture evaporates, cooling the pond. Nitrogen, dissolved primarily in the methane, exsolves, further cooling the liquid. However, because nitrogen is significantly more soluble in cooler methane-hydrocarbon mixtures, relatively more methane than nitrogen leaves the fluid, increasing the relative fraction of nitrogen. This increased nitrogen fraction increases the density of the liquid, as nitrogen is significantly denser than methane or ethane (pure ethane's density is intermediate to that of methane and nitrogen). At around 85 K the mixture is as dense as pure liquid ethane. Thus, further evaporative methane loss and cooling at the pond's surface leads to a chemical stratification, with an increasingly ethane rich epilimnion (surface layer) overlying a methane rich hypolimnion (subsurface layer). Further evaporation of methane from the ethane-rich epilimnion drives its temperature and composition toward the methane-ethane-nitrogen liquidus curve, causing pure ethane ice to precipitate out of solution and settle to the bottom of the pool. This settling would obscure the ethane ice from Cassini VIMS and ISS, which would instead continue to appear as a dark pond on the surface. As the ethane precipitates out completely, a binary methane-nitrogen liquid mixture remains

Pond Hockey on Whitmore Lacus: the Formation of Ponds and Ethane Ice Deposits Following Storm Events on Titan

Science.gov (United States)

Steckloff, Jordan; Soderblom, Jason M.

2017-10-01

Cassini ISS observations reveled regions, later identified as topographic low spots (Soderblom et al. 2014, DPS) on Saturn’s moon Titan become significantly darker (lower albedo) following storm events (Turtle et al. 2009, GRL; 2011, Science), suggesting pools of liquid hydrocarbon mixtures (predominantly methane-ethane-nitrogen). However, these dark ponds then significantly brighten (higher albedo relative to pre-storm albedo), before fading to their pre-storm albedos (Barnes et al. 2013 Planet. Sci; Soderblom et al. 2014, DPS). We interpret these data to be the result of ethane ice formation, which cools from evaporation of methane. The formation of ethane ices results from a unique sequence of thermophysical processes. Initially, the methane in the ternary mixture evaporates, cooling the pond. Nitrogen, dissolved primarily in the methane, exsolves, further cooling the liquid. However, because nitrogen is significantly more soluble in cooler methane-hydrocarbon mixtures, the relative concentration of nitrogen in the solution increases as it cools. This increased nitrogen fraction increases the density of the pond, as nitrogen is significantly more dense thane methane or ethane (pure ethane’s density is intermediate to that of methane and nitrogen). At around ~85 K the mixture is as dense as pure liquid ethane. Thus, further evaporative methane loss and cooling at the pond’s surface leads to a chemical stratification, with an increasingly ethane rich epilimnion (surface layer) overlying a methane rich hypolimnion (subsurface layer). Further evaporation of methane from the ethane-rich epilimnion drives its temperature and composition toward the methane-ethane-nitrogen liquidus curve, causing pure ethane ice to precipitate out of solution and settle to the bottom of the pool. This settling would obscure the ethane ice from Cassini VIMS and ISS, which would instead continue to appear as a dark pond on the surface. As the ethane precipitates out completely, a

Experimental and modeling investigations of solubility and saturated liquid densities and viscosities for binary systems (methane +, ethane +, and carbon dioxide + 2-propanol)

International Nuclear Information System (INIS)

Nourozieh, Hossein; Kariznovi, Mohammad; Abedi, Jalal

2013-01-01

Highlights: • Solubilities of CH 4 , C 2 H 6 , and CO 2 in 2-propanol and saturated density and viscosity. • Solubility of C 2 H 6 in 2-propanol is higher than CH 4 and CO 2 . • Dissolution of CO 2 increases liquid density and reduces liquid viscosity. • Liquid density and viscosity reduces with dissolution of CH 4 and C 2 H 6 . • Solubilities and saturated liquid densities were predicted with SRK and PR EOS. -- Abstract: Solubilities of methane, ethane, and carbon dioxide in 2-propanol have been measured at the temperatures (303 and 323) K and at the pressures up to 6 MPa using an in-house designed PVT apparatus. The saturated liquid properties, density and viscosity, were also measured in each experiment. Prior to the phase equilibrium measurements, the density and viscosity of pure 2-propanol were measured at the temperatures (303 and 323) K over the pressure range (0.1 to 10) MPa. The dissolution of carbon dioxide in 2-propanol caused a decline in the viscosity of saturated liquid phase while an increase in the density of gas-expanded liquid was observed. The viscosity-pressure trends for methane- and ethane-saturated liquid viscosities were similar to carbon dioxide, but the saturated liquid densities decreased with the dissolution of methane and ethane in 2-propanol. Solubility increased with pressure and decreased with temperature for all compressed gases (methane, ethane and carbon dioxide). The experimental data were well correlated using Soave–Redlich–Kwong and Peng–Robinson equations of state. The solubilities and saturated liquid densities were well represented with both equations of state, and there is no superior equation of state for the modeling of the phase compositions and saturated liquid densities

The effect of potassium addition to Pt supported on YSZ on steam reforming of mixtures of methane and ethane

NARCIS (Netherlands)

Graf, P.O.; Mojet, Barbara; Lefferts, Leonardus

2009-01-01

The influence of potassium addition on Pt supported on yttrium-stabilized zirconia (YSZ) was studied with FT-IR CO adsorption and CO-FT-IR-TPD, in order to understand the effect of potassium on the performance of the catalyst in reforming of mixtures of methane and ethane. Potassium modification of

AIRBORNE, OPTICAL REMOTE SENSING OF METHANE AND ETHANE FOR NATURAL GAS PIPELINE LEAK DETECTION

Energy Technology Data Exchange (ETDEWEB)

Jerry Myers

2003-11-12

Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. This second six-month technical report summarizes the progress made towards defining, designing, and developing the hardware and software segments of the airborne, optical remote methane and ethane sensor. The most challenging task to date has been to identify a vendor capable of designing and developing a light source with the appropriate output wavelength and power. This report will document the work that has been done to identify design requirements, and potential vendors for the light source. Significant progress has also been made in characterizing the amount of light return available from a remote target at various distances from the light source. A great deal of time has been spent conducting laboratory and long-optical path target reflectance measurements. This is important since it helps to establish the overall optical output requirements for the sensor. It also reduces the relative uncertainty and risk associated with developing a custom light source. The data gathered from the optical path testing has been translated to the airborne transceiver design in such areas as: fiber coupling, optical detector selection, gas filters, and software analysis. Ophir will next, summarize the design progress of the transceiver hardware and software development. Finally, Ophir will discuss remaining project issues that may impact the success of the project.

The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

NARCIS (Netherlands)

Swaan, H.M.; Swaan, H.M.; Li, X.; Seshan, Kulathuiyer; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

1993-01-01

The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

Science.gov (United States)

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Comparison between argon/methane and argon/ethane gas mixtures in cylindrical drift chambers operating in a high transverse magnetic field

International Nuclear Information System (INIS)

Binder, U.; Boer, W. de; Grindhammer, G.; Kotthaus, R.; Lierl, H.; Sack, B.

1983-03-01

We compare the behaviour of two commonly used gas mixtures argon/methane (90:10) and argon/ethane (50:50) in large cylindrical drift chambers operating in a transverse magnetic field of 1.3 T. The cooler gas argon/ethane was found to exhibit considerably smaller deflection angles, which in our case leads to an improved performance of the chambers. The deflection angles have been determined from a comparison of the experimental non-linear space time relation with the one calculated from a computer simulation of the drift process. For the simulation we use a simple model with only two free parameters. These two parameters are sufficient to obtain an accurate parametrization of the non-linear space time relation. (orig.)

Comparison between argon/methane and argon/ethane gas mixtures in cylindrical drift chambers operating in a high transverse magnetic field

International Nuclear Information System (INIS)

Binder, U.; De Boer, W.; Grindhammer, G.; Kotthaus, R.; Lierl, H.; Sack, B.

1983-01-01

We compare the behaviour of two commonly used gas mixture argon/methane (90:10) and argon/ethane (50:50) in large cylindrical drift chambers operating in a transverse magnetic field of 1.3 T. The cooler gas argon/ethane was found to exhibit considerably smaller deflection angles, which in our case leads to an improved performance of the chambers. The deflection angles have been determined from a comparison of the experimental non-linear space-time relation with the one calculated from a computer simulation of the drift process. For the simulation we use a simple model with only two free parameters. These two parameters are sufficient to obtain an accurate parametrization of the non-linear space-time relation. (orig.)

Methane oxidation and degradation of organic compounds in landfill soil covers

DEFF Research Database (Denmark)

Scheutz, Charlotte; Kjeldsen, Peter

2002-01-01

High rates of methane oxidation and degradation of the lowed halogenated methanes (TCM and DCM) and HCFCs (HCFC-21 and HCFC-22) were found in an investigation of the oxidation of methane and halogenated organic compunds (HOCs) in landfill gas affected soil. The degradation followed zero-order kin......High rates of methane oxidation and degradation of the lowed halogenated methanes (TCM and DCM) and HCFCs (HCFC-21 and HCFC-22) were found in an investigation of the oxidation of methane and halogenated organic compunds (HOCs) in landfill gas affected soil. The degradation followed zero...

Raman Spectra of Methane, Ethylene, Ethane, Dimethyl ether, Formaldehyde and Propane for Combustion Applications

KAUST Repository

Magnotti, G.

2015-05-09

Spontaneous Raman scattering measurements of temperature and major species concentration in hydrocarbon-air flames require detailed knowledge of the Raman spectra of the hydrocarbons present when fuels more complex than methane are used. Although hydrocarbon spectra have been extensively studied at room temperature, there are no data available at higher temperatures. Quantum mechanical calculations, when available are not sufficiently accurate for combustion applications. This work presents experimental measurements of spontaneous Stokes-Raman scattering spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane in the temperature range 300-860 K. Raman spectra from heated hydrocarbons jets have been collected with a higher resolution than is generally employed for Raman measurements in combustion applications. A set of synthetic spectra have been generated for each hydrocarbon, providing the basis for extrapolation to higher temperatures. The spectra provided here will enable simultaneous measurements of multiple hydrocarbons in flames. This capability will greatly extend the range of applicability of Raman measurements in combustion applications. In addition, the experimental spectra provide a validation dataset for quantum mechanical models.

Raman Spectra of Methane, Ethylene, Ethane, Dimethyl ether, Formaldehyde and Propane for Combustion Applications

KAUST Repository

Magnotti, G.; KC, Utsav; Varghese, P.L.; Barlow, R.S.

2015-01-01

Spontaneous Raman scattering measurements of temperature and major species concentration in hydrocarbon-air flames require detailed knowledge of the Raman spectra of the hydrocarbons present when fuels more complex than methane are used. Although hydrocarbon spectra have been extensively studied at room temperature, there are no data available at higher temperatures. Quantum mechanical calculations, when available are not sufficiently accurate for combustion applications. This work presents experimental measurements of spontaneous Stokes-Raman scattering spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane in the temperature range 300-860 K. Raman spectra from heated hydrocarbons jets have been collected with a higher resolution than is generally employed for Raman measurements in combustion applications. A set of synthetic spectra have been generated for each hydrocarbon, providing the basis for extrapolation to higher temperatures. The spectra provided here will enable simultaneous measurements of multiple hydrocarbons in flames. This capability will greatly extend the range of applicability of Raman measurements in combustion applications. In addition, the experimental spectra provide a validation dataset for quantum mechanical models.

Stratospheric ethane on Neptune - Comparison of groundbased and Voyager IRIS retrievals

Science.gov (United States)

Kostiuk, Theodor; Romani, Paul; Espenak, Fred; Bezard, Bruno

1992-01-01

Near-simultaneous ground and spacecraft measurements of 12-micron ethane emission spectra during the Voyager encounter with Neptune have furnished bases for the determination of stratospheric ethane abundance and the testing and constraining of Neptune methane-photochemistry models. The ethane retrievals were sensitive to the thermal profile used. Contribution functions for warm thermal profiles peaked at higher altitudes, as expected, with the heterodyne functions covering lower-pressure regions. Both constant- and nonconstant-with-height profiles remain candidate distributions for Neptune's stratospheric ethane.

Geodetic data support trapping of ethane in Titan's polar crust

Science.gov (United States)

Sotin, Christophe; Rambaux, Nicolas

2016-04-01

Titan's surface is characterized by polar depressions that strongly influence interpretations of the gravity data. This study investigates several geodynamical models that can explain these depressions. For each model, the values of the three moments of inertia are computed numerically by discretizing the interior in spherical coordinates. The study shows that a Pratt model where the polar subsurface is made of ethane clathrates can explain the polar depression, the abrupt jump in altitude at about 60 degrees latitude, and the values of the degree 2 gravity coefficients. This model, proposed by Choukroun and Sotin [1], is based on the stability of ethane clathrate hydrates relative to methane clathrate hydrates. In addition to fitting the geodetic data, it explains the absence of ethane in Titan's atmosphere although ethane is the main product of the photolysis of methane. Other geophysical models based on latitudinal variations in the tidal heating production or in the heat flux at the base of the icy crust do not provide such a good match to the gravity and topographic observations. The ethane-clathrate model predicts that all the ethane produced by photolysis of methane at the present rate during the last billion years could be stored in the polar subsurface. It is consistent with the age of Titan's surface and that of Titan's atmospheric methane inferred from geological and geochemical observations by the Cassini/Huygens mission. The present study also emphasizes the role of mass anomalies on the interpretation of the degree 2 gravity coefficients. It shows that for Titan, a slow rotator, the values of the two equatorial moments of inertia (MoI) are largely affected by the polar depressions whereas the value of polar MoI is not. Therefore, as pointed out by previous calculations [2], calculating the moment of inertia (MoI) factor from the value of J2 could lead to major errors. This is not the case for our preferred Titan's model for which the negative polar

Low-Temperature and Rapid Growth of Large Single-Crystalline Graphene with Ethane.

Science.gov (United States)

Sun, Xiao; Lin, Li; Sun, Luzhao; Zhang, Jincan; Rui, Dingran; Li, Jiayu; Wang, Mingzhan; Tan, Congwei; Kang, Ning; Wei, Di; Xu, H Q; Peng, Hailin; Liu, Zhongfan

2018-01-01

Future applications of graphene rely highly on the production of large-area high-quality graphene, especially large single-crystalline graphene, due to the reduction of defects caused by grain boundaries. However, current large single-crystalline graphene growing methodologies are suffering from low growth rate and as a result, industrial graphene production is always confronted by high energy consumption, which is primarily caused by high growth temperature and long growth time. Herein, a new growth condition achieved via ethane being the carbon feedstock to achieve low-temperature yet rapid growth of large single-crystalline graphene is reported. Ethane condition gives a growth rate about four times faster than methane, achieving about 420 µm min -1 for the growth of sub-centimeter graphene single crystals at temperature about 1000 °C. In addition, the temperature threshold to obtain graphene using ethane can be reduced to 750 °C, lower than the general growth temperature threshold (about 1000 °C) with methane on copper foil. Meanwhile ethane always keeps higher graphene growth rate than methane under the same growth temperature. This study demonstrates that ethane is indeed a potential carbon source for efficient growth of large single-crystalline graphene, thus paves the way for graphene in high-end electronical and optoelectronical applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ACCUMULATION OF POLY-B-HYDROXYBUTYRATE IN A METHANE- ENRICHED, HALOGENATED, HYDROCARBON-DEGRADING SOIL COLUMN: IMPLICATIONS FOR MICROBIAL COMMUNITY STRUCTURE AND NUTRITIONAL STATUS

Science.gov (United States)

The prokarotic, endogenous storage polymer poly--hydroxybutyrate (PHB) accumulated in soil from a methane-enriched, halogenated hydrocarbon-degrading soil column. Based on phospholipid ester-linked fatty acid (PLFA) profiles, this mocrocosm has been previously reported to be sign...

Solubility of carbon dioxide, methane, and ethane in 1-butanol and saturated liquid densities and viscosities

International Nuclear Information System (INIS)

Kariznovi, Mohammad; Nourozieh, Hossein; Abedi, Jalal

2013-01-01

Highlights: • Experimental solubilities of CH 4 , C 2 H 6 , and CO 2 in 1-butanol and saturated liquid properties. • Solubilities and saturated liquid densities were predicted with SRK and PR EOS. • Solubility of C 2 H 6 in 1-butanol is higher than CH 4 and CO 2 . • Liquid density and viscosity reduces with dissolution of CH 4 and C 2 H 6 . • Dissolution of CO 2 increases liquid density and reduces liquid viscosity. -- Abstract: A designed pressure–volume–temperature (PVT) apparatus has been used to measure the (vapor + liquid) equilibrium properties of three binary mixtures (methane +, ethane +, and carbon dioxide + 1-butanol) at two temperatures (303 and 323) K and at the pressures up to 6 MPa. The solubility of the compressed gases in 1-butanol and the saturated liquid densities and viscosities were measured. In addition, the density and viscosity of pure 1-butanol were measured at two temperatures (303 and 323) K and at the pressures up to 10 MPa. The experimental results show that the solubility of the gases in 1-butanol increases with pressure and decreases with temperature. The dissolution of gases in 1-butanol causes a decline in the viscosity of liquid phase. The saturated liquid density follows a decreasing trend with the solubility of methane and ethane. However, the dissolution of carbon dioxide in 1-butanol leads to an increase in the density of liquid phase. The experimental data are well correlated with Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR) equations of state (EOSs). SRK EOS was slightly superior for correlating the saturated liquid densities

Discrepancy between simulated and observed ethane and propane levels explained by underestimated fossil emissions

Science.gov (United States)

Dalsøren, Stig B.; Myhre, Gunnar; Hodnebrog, Øivind; Myhre, Cathrine Lund; Stohl, Andreas; Pisso, Ignacio; Schwietzke, Stefan; Höglund-Isaksson, Lena; Helmig, Detlev; Reimann, Stefan; Sauvage, Stéphane; Schmidbauer, Norbert; Read, Katie A.; Carpenter, Lucy J.; Lewis, Alastair C.; Punjabi, Shalini; Wallasch, Markus

2018-03-01

Ethane and propane are the most abundant non-methane hydrocarbons in the atmosphere. However, their emissions, atmospheric distribution, and trends in their atmospheric concentrations are insufficiently understood. Atmospheric model simulations using standard community emission inventories do not reproduce available measurements in the Northern Hemisphere. Here, we show that observations of pre-industrial and present-day ethane and propane can be reproduced in simulations with a detailed atmospheric chemistry transport model, provided that natural geologic emissions are taken into account and anthropogenic fossil fuel emissions are assumed to be two to three times higher than is indicated in current inventories. Accounting for these enhanced ethane and propane emissions results in simulated surface ozone concentrations that are 5-13% higher than previously assumed in some polluted regions in Asia. The improved correspondence with observed ethane and propane in model simulations with greater emissions suggests that the level of fossil (geologic + fossil fuel) methane emissions in current inventories may need re-evaluation.

Dissociation of ethane by electron impact

International Nuclear Information System (INIS)

Winters, H.F.

1979-01-01

The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 X 10 -16 cm 2 occurs at 80 eV while the apparent threshold is approximately 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (e - +C 2 H 6 → CH 4 + CH 2 ) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation. (Auth.)

Isotopic studies on oxidative methane coupling over samarium oxide

International Nuclear Information System (INIS)

Otsuka, Kiyoshi; Inaida, Masakatsu; Wada, Yuji; Komatsu, Takayuki; Morikawa, Akira

1989-01-01

The evident kinetic isotope effect was observed for the formations of ethylene and ethane through the oxidative coupling of methane on Sm 2 O 3 , when CH 4 and CD 4 were used as the reactants. Ethanes formed in the reaction of a mixture of CH 4 , CD 4 , and O 2 were C 2 H 6 , C 2 H 3 D 3 , and C 2 D 6 as major products. These results indicate that the rate-determining step of the reaction is abstraction of hydrogen from methane and that ethane is formed through the coupling of methyl intermediate. (author)

Self- and air-broadened cross sections of ethane (C2H6) determined by frequency-stabilized cavity ring-down spectroscopy near 1.68 µm

International Nuclear Information System (INIS)

Reed, Zachary D.; Hodges, Joseph T.

2015-01-01

The absorption spectrum of ethane was measured by frequency-stabilized cavity ring-down spectroscopy over the wave number range 5950–5967 cm −1 . Spectra are reported for both pure ethane acquired at pressures near 3 Pa and mixtures of ethane in air at pressures ranging from 666 Pa to 101.3 kPa. Absorption cross sections are reported with a spectrum sampling period of 109 MHz and frequency resolution of 200 kHz. Atmospheric pressure cross sections agree fairly well with existing cross sections determined by FTS in nitrogen, but there are significant variations in cross sections at lower pressures. Source identification of fugitive methane emissions using spectroscopic measurements of the atmospheric ethane-to-methane ratio is also discussed. - Highlights: • We measured spectra of pure and air-broadened ethane in the 1.7 μm region. • Measured cross sections were substantially different than literature values. • Relative uncertainties of measured cross sections were less than 1 %. • These results can be used to quantify ethane/methane ratios for source apportionment

Solubility of Methane, Ethane, and Propane in Pure Water Using New Binary Interaction Parameters

Directory of Open Access Journals (Sweden)

Masoud Behrouz

2015-07-01

Full Text Available Solubility of hydrocarbons in water is important due to ecological concerns and new restrictions on the existence of organic pollutants in water streams. Also, the creation of a thermodynamic model has required an advanced study of the phase equilibrium between water (as a basis for the widest spread muds and amines and gas hydrocarbon phases in wide temperature and pressure ranges. Therefore, it is of great interest to develop semi-empirical correlations, charts, or thermodynamic models for estimating the solubility of hydrocarbons in liquid water. In this work, a thermodynamic model based on Mathias modification of Sova-Redlich-Kwong (SRK equation of state is suggested using classical mixing rules with new binary interaction parameters which were used for two-component systems of hydrocarbons and water. Finally, the model results and their deviations in comparison with the experimental data are presented; these deviations were equal to 5.27, 6.06, and 4.1% for methane, ethane, and propane respectively.

In situ high temperature MAS NMR study of the mechanisms of catalysis. Ethane aromatization on Zn-modified zeolite BEA.

Science.gov (United States)

Arzumanov, Sergei S; Gabrienko, Anton A; Freude, Dieter; Stepanov, Alexander G

2009-04-01

Ethane conversion into aromatic hydrocarbons over Zn-modified zeolite BEA has been analyzed by high-temperature MAS NMR spectroscopy. Information about intermediates (Zn-ethyl species) and reaction products (mainly toluene and methane), which were formed under the conditions of a batch reactor, was obtained by (13)C MAS NMR. Kinetics of the reaction, which was monitored by (1)H MAS NMR in situ at the temperature of 573K, provided information about the reaction mechanism. Simulation of the experimental kinetics within the frames of the possible kinetic schemes of the reaction demonstrates that a large amount of methane evolved under ethane aromatization arises from the stage of direct ethane hydrogenolysis.

Effect of alloying on carbon formation during ethane dehydrogenation

DEFF Research Database (Denmark)

Rovik, Anne; Kegnæs, Søren; Dahl, Søren

2009-01-01

The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested in the c......The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested...... in the conversion of ethane. A tendency is clear for all catalysts: In the first period of time 100% ethane is converted and roughly half of the carbon is converted into coke and deposited on the catalyst. The other half of the carbon is converted into methane. The active sites in the hydrogenolysis are blocked...... by coke during the initial period where after dehydrogenation of ethane is observed. It has previously been predicted in surface science studies that Ag covers the steps of certain transition metals. Here it is documented that the hydrogenolysis and coking reactions are significantly suppressed by co...

Methane distribution and methane oxidation in the water column of the Elbe estuary, Germany

Czech Academy of Sciences Publication Activity Database

Matoušů, Anna; Osudar, R.; Šimek, Karel; Bussmann, I.

2017-01-01

Roč. 79, č. 3 (2017), s. 443-458 ISSN 1015-1621 R&D Projects: GA ČR(CZ) GA13-00243S Institutional support: RVO:60077344 Keywords : estuary * methane * methane budget * ethane oxidation * River Elbe Subject RIV: DA - Hydrology ; Limnology OBOR OECD: Marine biology, freshwater biology, limnology Impact factor: 2.821, year: 2016

Assessing the long-term variability of acetylene and ethane in the stratosphere of Jupiter

Science.gov (United States)

Melin, Henrik; Fletcher, L. N.; Donnelly, P. T.; Greathouse, T. K.; Lacy, J. H.; Orton, G. S.; Giles, R. S.; Sinclair, J. A.; Irwin, P. G. J.

2018-05-01

Acetylene (C2H2) and ethane (C2H6) are both produced in the stratosphere of Jupiter via photolysis of methane (CH4). Despite this common source, the latitudinal distribution of the two species is radically different, with acetylene decreasing in abundance towards the pole, and ethane increasing towards the pole. We present six years of NASA IRTF TEXES mid-infrared observations of the zonally-averaged emission of methane, acetylene and ethane. We confirm that the latitudinal distributions of ethane and acetylene are decoupled, and that this is a persistent feature over multiple years. The acetylene distribution falls off towards the pole, peaking at ∼ 30°N with a volume mixing ratio (VMR) of ∼ 0.8 parts per million (ppm) at 1 mbar and still falling off at ± 70° with a VMR of ∼ 0.3 ppm. The acetylene distributions are asymmetric on average, but as we move from 2013 to 2017, the zonally-averaged abundance becomes more symmetric about the equator. We suggest that both the short term changes in acetylene and its latitudinal asymmetry is driven by changes to the vertical stratospheric mixing, potentially related to propagating wave phenomena. Unlike acetylene, ethane has a symmetric distribution about the equator that increases toward the pole, with a peak mole fraction of ∼ 18 ppm at about ± 50° latitude, with a minimum at the equator of ∼ 10 ppm at 1 mbar. The ethane distribution does not appear to respond to mid-latitude stratospheric mixing in the same way as acetylene, potentially as a result of the vertical gradient of ethane being much shallower than that of acetylene. The equator-to-pole distributions of acetylene and ethane are consistent with acetylene having a shorter lifetime than ethane that is not sensitive to longer advective timescales, but is augmented by short-term dynamics, such as vertical mixing. Conversely, the long lifetime of ethane allows it to be transported to higher latitudes faster than it can be chemically depleted.

ESR studies of Bunsen-type methane-air flames. II. The effects of the addition of halogenated compounds to the secondary air on the hydrogen atoms in the flame

Energy Technology Data Exchange (ETDEWEB)

Noda, S; Fujimoto, S; Claesson, O; Yoshida, H

1983-09-01

Hydrogen atoms in a methane-air Bunsen-type flame were detected by the flame-in-cavity ESR method. The addition of a halogenated compound to the secondary air reduced the H-atom concentration linearly with an increase in additive concentration. These 8 halogenated compounds examined showed increased effectiveness in scavenging H atoms in this order: hydrochloric acid < dichlorodifluoromethane < chloroform < methyl chloride < methylene chloride < trichlorofluoromethane < carbon tetrachlorie < methyl bromide. The chemical effects of these additives on the combustion reactions agree well with the inhibitor indices for these compounds. 14 references, 3 figures.

Low-Latitude Ethane Rain on Titan

Science.gov (United States)

Dalba, Paul A.; Buratti, Bonnie J.; Brown, R. H.; Barnes, J. W.; Baines, K. H.; Sotin, C.; Clark, R. N.; Lawrence, K. J.; Nicholson, P. D.

2012-01-01

Cassini ISS observed multiple widespread changes in surface brightness in Titan's equatorial regions over the past three years. These brightness variations are attributed to rainfall from cloud systems that appear to form seasonally. Determining the composition of this rainfall is an important step in understanding the "methanological" cycle on Titan. I use data from Cassini VIMS to complete a spectroscopic investigation of multiple rain-wetted areas. I compute "before-and-after" spectral ratios of any areas that show either deposition or evaporation of rain. By comparing these spectral ratios to a model of liquid ethane, I find that the rain is most likely composed of liquid ethane. The spectrum of liquid ethane contains multiple absorption features that fall within the 2-micron and 5-micron spectral windows in Titan's atmosphere. I show that these features are visible in the spectra taken of Titan's surface and that they are characteristically different than those in the spectrum of liquid methane. Furthermore, just as ISS saw the surface brightness reverting to its original state after a period of time, I show that VIMS observations of later flybys show the surface composition in different stages of returning to its initial form.

Co-conversion of Ethane and Methanol into Higher Hydrocarbons over Ga/H-ZSM-5, Mo/H-ZSM-5 and Ga-Mo/H-ZSM-5

DEFF Research Database (Denmark)

Mentzel, Uffe Vie; Rovik, Anne; Christensen, Claus H.

2009-01-01

Ethane and methanol are converted simultaneously over Ga/H-ZSM-5, Mo/H-ZSM-5 and Ga-Mo/H-ZSM-5 to produce light olefins and aromatics. The presence of methanol in the reactant stream is intended to facilitate activation of ethane following literature reports on co-conversion of methane and methan...... and in the carbonaceous compounds deposited on the catalysts. This indicates that both reactants take part in the formation of the hydrocarbon pool, which is the origin of all products....

The MOYA aircraft campaign: First measurements of methane, ethane and C-13 isotopes from West African biomass burning and other regional sources using the UK FAAM aircraft

Science.gov (United States)

Allen, Grant; Pitt, Joseph; Lee, James; Hopkins, James; Young, Stuart; Bauguitte, Stéphane; Gallagher, Martin; Fisher, Rebecca; Lowry, David; Nisbet, Euan

2017-04-01

Global methane concentrations continue to rise due to an imbalance between sources and sinks. There remains little consensus on the relative components of the manifold source types and their geographical origin. The Global Methane Budget and Yearly Assessments (MOYA) project is tasked with better characterising the global methane budget through an augmented global measurement and modelling programme. As part of MOYA, the UK's Facility for Airborne Atmospheric Measurement (FAAM), will fly four campaigns based out of West Africa and Ascension Island in the period 2017-2019, to focus on the important role of tropical sources. The first of these, to be conducted in late February 2017, will focus on the biomass burning season in West Africa. This paper will present the plan for future FAAM MOYA campaigns and report on our first aircraft data gathered in the West African region. The new addition of an interband cascade laser spectrometer to the FAAM aircraft, flown in this campaign for the first time, promises to provide the first real-time, continuous, and simultaneous, airborne measurements of methane, ethane and methane C-13 isotopologues. Together, these measurements, when interpreted in combination with other trace gases and aerosol measured on the aircraft, will serve as case studies to inform modelling of regional and global fluxes through their isotopic fingerprints.

Electron transport in liquids: effect of unbalancing the methane molecule by deuteration

International Nuclear Information System (INIS)

Floriano, M.A.; Freeman, G.R.

1983-01-01

The mobility of electrons in nonpolar liquids is strongly dependent on the molecular shape. In spherelike methane the mobility is three orders of magnitude greater than in the rodlike ethane. To investigate the enormous gap between methane and ethane, the effect of slightly perturbing the symmetry of the methane molecule by progressive deuterium substitution was studied. At temperatures near the triple point (T/Tsub(c) approximately 0.48) and near the mobility maximum (T/Tsub(c) approximately 0.93) the mobilities change in the order: CH 4 > CH 3 D > CH 2 D 2 3 approximately CD 4 . The differences are related to the symmetries of the molecules and to the rotational motions. (Authors)

Process for producing ethane and/or ethylene from methane. Verfahren zur Herstellung von Ethan und bzw. oder Ethylen aus Methan

Energy Technology Data Exchange (ETDEWEB)

Baerns, M.; Hinsen, W.

1984-04-12

According to the invention, methane is converted into hydrocarbons with oxygen with high selectivity. This is done in the presence of a catalyst fluidized in a fluidized bed - preferably lead oxide or a mixture of this with antimony oxide - at temperatures between 600 and 800/sup 0/C and at oxygen partial pressures preferably below 0.1-0.2 bar. The ratio of methane partial pressure to oxygen partial pressure should be greater than 2 to 5 if possible. The reactor is operated with gas feedback, in order to raise the selectivity even more.

A post-Cassini view of Titan's methane-based hydrologic cycle

Science.gov (United States)

Hayes, Alexander G.; Lorenz, Ralph D.; Lunine, Jonathan I.

2018-05-01

The methane-based hydrologic cycle on Saturn's largest moon, Titan, is an extreme analogue to Earth's water cycle. Titan is the only planetary body in the Solar System, other than Earth, that is known to have an active hydrologic cycle. With a surface pressure of 1.5 bar and temperatures of 90 to 95 K, methane and ethane condense out of a nitrogen-based atmosphere and flow as liquids on the moon's surface. Exchange processes between atmospheric, surface and subsurface reservoirs produce methane and ethane cloud systems, as well as erosional and depositional landscapes that have strikingly similar forms to their terrestrial counterparts. Over its 13-year exploration of the Saturn system, the Cassini-Huygens mission revealed that Titan's hydrocarbon-based hydrology is driven by nested methane cycles that operate over a range of timescales, including geologic, orbital (for example, Croll-Milankovitch cycles), seasonal and that of a single convective storm. In this Review Article, we describe the dominant exchange processes that operate over these timescales and present a post-Cassini view of Titan's methane-based hydrologic system.

Parametric performance of circumferentially grooved heat pipes with homogeneous and graded-porosity slab wicks at cryogenic temperatures. [methane and ethane working fluids

Science.gov (United States)

Groll, M.; Pittman, R. B.; Eninger, J. E.

1976-01-01

A recently developed, potentially high-performance nonarterial wick was extensively tested. This slab wick has an axially varying porosity which can be tailored to match the local stress imposed on the wick. The purpose of the tests was to establish the usefulness of the graded-porosity slab wick at cryogenic temperatures between 110 and 260 K, with methane and ethane as working fluids. For comparison, a homogeneous (i.e., uniform porosity) slab wick was also tested. The tests included: maximum heat pipe performance as a function of fluid inventory, maximum performance as a function of operating temperature, maximum performance as a function of evaporator elevation, and influence of slab wick orientation on performance. The experimental data were compared with theoretical predictions obtained with the GRADE computer program.

Cage occupancies of natural gas hydrates encaging methane and ethane

Energy Technology Data Exchange (ETDEWEB)

Kida, M.; Hachikubo, A.; Sakagami, H.; Minami, H.; Krylov, A.; Yamashita, S.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan); Khlystov, O. [Limnological Inst., Irkutsk (Russian Federation). Siberian Branch of the Russian Academy of Sciences; Poort, J. [Ghent Univ., Ghent (Belgium). Renard Centre of Marine Geology; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan)

2008-07-01

Natural gas hydrates are crystalline compounds that contain large amounts of natural gas in its structure and are expected to provide natural gas resources in the future. The gas species are trapped in different types of polyhedral cages which consist of hydrogen bonded water molecules. Three main types of crystallographic structures exist, notably structure 1, structure 2 and structure H (sH). The crystallographic structure of natural gas hydrates depends on the encaged gas components. The cage occupancy is the ratio of the number of cages occupied by guest molecules to the number of total cages. It is also important to estimate the amount of natural gas, since it depends on the condition of the hydrate formation such as gas composition. The cages of natural gas hydrates mainly contain methane. However, other heavier hydrocarbons such as ethane (C{sub 2}H{sub 6}), propane (C{sub 3}H{sub 8}), and isobutane (i-C{sub 4}H{sub 1}0) may be encaged together with CH{sub 4}. Little is known about cage occupancies of natural gas hydrates including CH{sub 4} and heavier hydrocarbons. This paper discussed a study that developed cage occupancy estimations of natural gas hydrates encaging heavier hydrocarbons. 13C nuclear magnetic resonance (NMR) measurements were conducted. The assignments of resonance lines were based on 13C chemical shifts obtained by artificial sample measurements. The paper presented the experimental data and discussed the results of the study. The large cages were almost fully occupied with CH{sub 4} and C{sub 2}H{sub 6} molecules, whereas the small cage occupancies of CH{sub 4} were below 0.8. The distribution of CH{sub 4} and C{sub 2}H{sub 6} in each cage were similar to that of synthetic CH{sub 4} + C{sub 2}H{sub 6} hydrate. It was concluded that these results should be useful for optimal estimation of the amount of natural gas in gas hydrates. 18 refs., 1 tab., 3 figs.

A numerical analysis of heat and mass transfer during the steam reforming process of ethane

Science.gov (United States)

Tomiczek, Marcin; Kaczmarczyk, Robert; Mozdzierz, Marcin; Brus, Grzegorz

2017-11-01

This paper presents a numerical analysis of heat and mass transfer during the steam reforming of ethane. From a chemical point of view, the reforming process of heavy hydrocarbons, such as ethane, is complex. One of the main issue is a set of undesired chemical reactions that causes the deposition of solid carbon and consequently blocks the catalytic property of a reactor. In the literature a carbon deposition regime is selected by thermodynamical analysis to design safe operation conditions. In the case of Computational Fluid Dynamic (CFD, hereafter) models each control volume should be investigated to determinate if carbon deposition is thermodynamically favourable. In this paper the authors combine equilibrium and kinetics analysis to simulate the steam reforming of methane-ethane rich fuel. The results of the computations were juxtaposed with experimental data for methane steam reforming, and good agreement was found. An analysis based on the kinetics of reactions was conducted to predict the influence of temperature drop and non-equilibrium composition on solid carbon deposition. It was found that strong non-uniform temperature distribution in the reactor causes conditions favourable for carbon deposition at the inlet of the reformer. It was shown that equilibrium calculations, often used in the literature, are insufficient.

Methane Emissions from Natural Gas in the Urban Region of Boston, Massachusetts

Science.gov (United States)

McKain, K.; Down, A.; Raciti, S. M.; Budney, J.; Hutyra, L.; Floerchinger, C. R.; Herndon, S. C.; Zahniser, M. S.; Nehrkorn, T.; Jackson, R. B.; Phillips, N. G.; Wofsy, S. C.

2014-12-01

Methane emissions from the natural gas supply chain must be quantified to assess environmental impacts of natural gas and to develop emission reduction strategies. We report natural gas emission rates for one year in the urban region of Boston, MA, using an atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission rate, 20.6 ± 1.7 (95 % CI) g CH4 m-2 yr-1. Simultaneous observations of atmospheric ethane, compared with the ethane to methane ratio in pipeline gas, demonstrate that natural gas accounted for 58 - 100 % of methane emissions, depending on season. Using government statistics and geospatial data on energy consumption, we estimate the fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end-use, was 2.9 ± 0.3 % in the Boston urban region, compared to 1.1 % inferred by the Massachusetts greenhouse gas inventory.

The relative reactivities of ethane, ethane-d6, n-butane and neopentane towards 'hot' tritium atoms

International Nuclear Information System (INIS)

Urch, D.S.; Welch, M.J.

1974-01-01

The reactions of recoil tritium with ethane-butane, and ethane-neopentane mixtures have been studied in the presence and absence of helium moderator. It is shown that the larger molecules are labelled by recoil atoms of a higher mean energy than those which label ethane. It is also shown that hydrogen atoms at CH 2 sites are replaced by higher energy tritium atoms than those at CH 3 sites. An analogy is drawn with the abstraction reaction and a simple unified model for high-energy recoil tritium reactions at a C-H site is proposed. The more complex the other groups attached to the carbon the greater the mean energy of the recoil atoms reacting with the C-H bond. Experiments with ethane-d 6 established that the primary isotope effect for abstraction is comparable to that for displacement with a value of 1.25 approximately 1.30. (orig.) [de

Electron spin resonance study on γ-ray-induced ethyl radical in ethane hydrate

International Nuclear Information System (INIS)

Takeya, Kei; Nango, Kouhei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi; Ito, Hironori; Okada, Michio; Kasai, Toshio

2007-01-01

Electron spin resonance (ESR) studies have been performed to investigate radicals induced in ethane hydrate irradiated by γ-rays at 77K. Two ESR spectra are observed and identified as the induced ethyl radical (g=2.0031±0.0005, A α sub(perpendicular)=2.2±0.1mT, A α sub(parallel)=2.5±0.1mT, A β =2.7±0.1mT) and induced atomic hydrogen (g=2.0026±0.0005, A=50.5±0.1mT). From the results of ESR analysis and gas mass spectroscopy, it is concluded that the ethyl radical decays into butane by dimerization in the first-order reaction in the temperature region of 250-265K. The activation energy of the decay reaction is 73.1±6.3kJ/mol, which is near the dissociation enthalpy change of ethane hydrate to liquid water and gaseous ethane. This finding implies that ethane hydrate does not dissociate into ice but supercooled water in the present temperature region, similar to the dissociation of methane hydrate in our previous study. (author)

Preliminary scattering kernels for ethane and triphenylmethane at cryogenic temperatures

Science.gov (United States)

Cantargi, F.; Granada, J. R.; Damián, J. I. Márquez

2017-09-01

Two potential cold moderator materials were studied: ethane and triphenylmethane. The first one, ethane (C2H6), is an organic compound which is very interesting from the neutronic point of view, in some respects better than liquid methane to produce subthermal neutrons, not only because it remains in liquid phase through a wider temperature range (Tf = 90.4 K, Tb = 184.6 K), but also because of its high protonic density together with its frequency spectrum with a low rotational energy band. Another material, Triphenylmethane is an hydrocarbon with formula C19H16 which has already been proposed as a good candidate for a cold moderator. Following one of the main research topics of the Neutron Physics Department of Centro Atómico Bariloche, we present here two ways to estimate the frequency spectrum which is needed to feed the NJOY nuclear data processing system in order to generate the scattering law of each desired material. For ethane, computer simulations of molecular dynamics were done, while for triphenylmethane existing experimental and calculated data were used to produce a new scattering kernel. With these models, cross section libraries were generated, and applied to neutron spectra calculation.

Observation and simulation of ethane at 23 FTIR sites

Science.gov (United States)

Bader, W. M. J.; Mahieu, E.; Franco, B.; Pozzer, A.; Taraborrelli, D.; Prignon, M.; Servais, C. P.; De Maziere, M.; Vigouroux, C.; Mengistu Tsidu, G.; Sufa, G.; Mellqvist, J.; Blumenstock, T.; Hase, F.; Schneider, M.; Sussmann, R.; Nagahama, T.; Sudo, K.; Hannigan, J. W.; Ortega, I.; Morino, I.; Nakajima, H.; Smale, D.; Makarova, M.; Poberovsky, A.; Murata, I.; Grutter de la Mora, M.; Guarin, C. A.; Stremme, W.; Té, Y.; Jeseck, P.; Notholt, J.; Palm, M.; Conway, S. A.; Lutsch, E.; Strong, K.; Griffith, D. W. T.; Jones, N. B.; Paton-Walsh, C.; Friedrich, M.; Smeekes, S.

2017-12-01

Ethane is the most abundant non-methane hydrocarbon (NMHC) in the Earth atmosphere. Its main sources are of anthropogenic origin, with globally 62% from leakage during production and transport of natural gas, 20% from biofuel combustion and 18% from biomass burning. In the Southern hemisphere, anthropogenic emissions are lower which makes biomass burning emissions a more significant source. The main removal process is oxidation by the hydroxyl radical (OH), leading to a mean atmospheric lifetime of 2 months. Until recently, a prolonged decrease of its abundance has been documented, at rates of -1 to -2.7%/yr, with global emissions dropping from 14 to 11 Tg/yr over 1984-2010 owing to successful measures reducing fugitive emissions from its fossil fuel sources. However, subsequent investigations have reported on an upturn in the ethane trend, characterized by a sharp rise from about 2009 onwards. The ethane increase is attributed to the oil and natural gas production boom in North America, although significant changes in OH could also be at play. In the present contribution, we report the trend of ethane at 23 ground-based Fourier Transform Infrared (FTIR) sites spanning the 80ºN to 79ºS latitude range. Over 2010-2015, a significant ethane rise of 3-5%/yr is determined for most sites in the Northern Hemisphere, while for the Southern hemisphere the rates of changes are not significant at the 2-sigma uncertainty level . Dedicated model simulations by EMAC (ECHAM5/MESSy Atmospheric Chemistry; 1.8×1.8 degrees) implementing various emission scenarios are included in order to support data interpretation. The usual underestimation of the NMHCs emissions in the main inventories is confirmed here for RCP85 (Representative Concentration Pathway Database v8.5). Scaling them by 1.5 is needed to capture the background levels of atmospheric ethane. Moreover, additional and significant emissions ( 7 Tg over 2009-2015) are needed to capture the ethane rise in the Northern

Kinetics of the reaction of hydroxyl radicals with ethane and a series of Cl- and F-substituted methanes at 300-400degK

International Nuclear Information System (INIS)

Bjarnov, E.; Munk, J.; Nielsen, O.J.; Pagsberg, P.; Sillesen, A.

1982-04-01

Gas phase reactions of hydroxyl radicals with ethane and a series of Cl- and F-substituted methanes were studied at atmospheric pressure and over the temperature range 300-400degK. Hydroxyl radicals were produced by pulse radiolysis of water vapour and the decay rate was studied by monitoring the transient light absorption at 3090 A. Arrhenius parameters (A,Esub(a)) for the reaction RH + OH arrow R + HOH were obtained for the reactants RH = C 2 H 6 ,CH 3 Cl,CH 2 Cl 2 ,CHFCl 2 . CF 2 Cl 2 (CFC-12) which contains no C-H bonds was found to be inert toward attack by hydroxyl radicals. Since no other tropospheric sink reactions have been reported for CFC-12 its possible impact on the stratospheric ozone remains a controversial problem. (author)

Electrocatalytic oxidation of methane: investigations of new catalysts to be used in a solid polymer electrolyte methane fuel-cell; Oxydation electrocatalytique du methane: recherche de catalyseurs en vue d'une application a une pile au methane a electrolyte polymere solide

Energy Technology Data Exchange (ETDEWEB)

Berthelot, S

1998-07-01

This thesis evaluated the performances of many catalysts facing the methane oxidation which is a critical step in methane fuel cells development. In a first part the study of the methane electro-oxidation has been realized by classical electrochemical technics on many electrodes to determine the most active ones. In a second part the in situ reflection infra-red spectroscopy allowed to identify, during the methane oxidation, the adsorbed species on the electrode and the reaction products. These results also help the understanding of the part of the concerned materials mechanisms in the methane oxidation and then to optimize them for a whole oxidation of the methane in carbon dioxide. The final objective is the use of the methane in a PEMFC fuel cell type. A comparison with the methanol and C2 hydrocarbons behaviour, such as the ethane the ethylene and the acetylene, has been done to evaluate the performances. (A.L.B.)

Reduced biomass burning emissions reconcile conflicting estimates of the post-2006 atmospheric methane budget.

Science.gov (United States)

Worden, John R; Bloom, A Anthony; Pandey, Sudhanshu; Jiang, Zhe; Worden, Helen M; Walker, Thomas W; Houweling, Sander; Röckmann, Thomas

2017-12-20

Several viable but conflicting explanations have been proposed to explain the recent ~8 p.p.b. per year increase in atmospheric methane after 2006, equivalent to net emissions increase of ~25 Tg CH 4 per year. A concurrent increase in atmospheric ethane implicates a fossil source; a concurrent decrease in the heavy isotope content of methane points toward a biogenic source, while other studies propose a decrease in the chemical sink (OH). Here we show that biomass burning emissions of methane decreased by 3.7 (±1.4) Tg CH 4 per year from the 2001-2007 to the 2008-2014 time periods using satellite measurements of CO and CH 4 , nearly twice the decrease expected from prior estimates. After updating both the total and isotopic budgets for atmospheric methane with these revised biomass burning emissions (and assuming no change to the chemical sink), we find that fossil fuels contribute between 12-19 Tg CH 4 per year to the recent atmospheric methane increase, thus reconciling the isotopic- and ethane-based results.

Canadian ethane market overview

Energy Technology Data Exchange (ETDEWEB)

Stauft, T. [TransCanada Midstream, Calgary, AB (Canada)

1999-07-01

A review of the Canadian petrochemical industry, the supply and demand for ethane, and the longer-term outlook for ethane are presented. Recent projections of natural gas production by the National Energy Board are examined, along with the impact on ethane supply and demand by Alliance. It is suggested that reduced gas will flow past Cochrane and Empress, Alberta ethane and gas prices will increase relative to US Gulf Coast prices, and since expansion is based on ethane demand, the combined influence of these factors will be to delay the construction of new extraction capacity. Present capacity is considered sufficient to produce ethane for the current round of petrochemical plant expansions. Excess supplies will exist for the next few years, and Alberta ethane prices are likely to strengthen due to the tight supply/demand balance. The combination of the impact of the Alliance Pipeline project and the ultimate potential of the Western Canadian Sedimentary Basin are the major uncertainties. On the plus side, both the US and Canadian regulatory agencies appear to be moving away from regulating ethane, and towards allowing a competitive market to develop.

Canadian ethane market overview

International Nuclear Information System (INIS)

Stauft, T.

1999-01-01

A review of the Canadian petrochemical industry, the supply and demand for ethane, and the longer-term outlook for ethane are presented. Recent projections of natural gas production by the National Energy Board are examined, along with the impact on ethane supply and demand by Alliance. It is suggested that reduced gas will flow past Cochrane and Empress, Alberta ethane and gas prices will increase relative to US Gulf Coast prices, and since expansion is based on ethane demand, the combined influence of these factors will be to delay the construction of new extraction capacity. Present capacity is considered sufficient to produce ethane for the current round of petrochemical plant expansions. Excess supplies will exist for the next few years, and Alberta ethane prices are likely to strengthen due to the tight supply/demand balance. The combination of the impact of the Alliance Pipeline project and the ultimate potential of the Western Canadian Sedimentary Basin are the major uncertainties. On the plus side, both the US and Canadian regulatory agencies appear to be moving away from regulating ethane, and towards allowing a competitive market to develop

Preliminary scattering kernels for ethane and triphenylmethane at cryogenic temperatures

Directory of Open Access Journals (Sweden)

Cantargi F.

2017-01-01

Full Text Available Two potential cold moderator materials were studied: ethane and triphenylmethane. The first one, ethane (C2H6, is an organic compound which is very interesting from the neutronic point of view, in some respects better than liquid methane to produce subthermal neutrons, not only because it remains in liquid phase through a wider temperature range (Tf = 90.4 K, Tb = 184.6 K, but also because of its high protonic density together with its frequency spectrum with a low rotational energy band. Another material, Triphenylmethane is an hydrocarbon with formula C19H16 which has already been proposed as a good candidate for a cold moderator. Following one of the main research topics of the Neutron Physics Department of Centro Atómico Bariloche, we present here two ways to estimate the frequency spectrum which is needed to feed the NJOY nuclear data processing system in order to generate the scattering law of each desired material. For ethane, computer simulations of molecular dynamics were done, while for triphenylmethane existing experimental and calculated data were used to produce a new scattering kernel. With these models, cross section libraries were generated, and applied to neutron spectra calculation.

High-Resolution Spectroscopy of Stratospheric Ethane Following the Jupiter Impact of 2009

Science.gov (United States)

Fast, Kelly; Kostiuk, Theodor; Livengood, Timothy A.; Hewagama, Tilak; Amen, John

2010-01-01

We report on high-resolution infrared spectroscopy of ethane (C2H6) performed at the latitude of an impact site on Jupiter discovered on 19 July 2009 by A. Wesley from a location in Murrumbateman, Australia. The observations used the NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii. HIPWAC is a mid-infrared (9-12 microns) heterodyne spectrometer operating at the highest limit of spectral resolving power (lambda\\Delta\\lambda > l06), providing information on atmospheric constituent abundance and temperature through fully resolved tine shapes. Ethane is a stable trace product of methane photochemistry that is nearly uniformly mixed in Jupiter's stratosphere, providing an effective probe of that altitude region. Ethane emission line profiles near 11,74 microns in the Ug band were measured in Jupiter's stratosphere at 25 MHz (11.00083/cm) resolution. A sequence of spectra of ethane acquired over a range of longitude at the impact latitude (56S planetocentric) probes constituent abundance and temperature profile, both on and off the impact region. Near the site of the impact, ethane emission increased above levels measured well outside the impact region. Radiative transfer analysis indicates increased ethane mole fraction (30% greater). Variation in the measured continuum level and line intensities within 75deg of the impact longitude indicate the presence of an opacity source (haze) at altitudes near and above the tropopause and as high as the 10-mbar level near the impact site. The indication of possible haze opacity up to the 10-mbar level in the atmosphere is consistent with measurements made by HIPWAC's predecessor as part of the IRTF Shoemaker Levy-9 campaign in 1994.

An Atmosphere-based Method for Detection and Quantification of Methane Emisions from Natural Gas Infrastructure in an Urban Environment

Science.gov (United States)

McKain, K.; Down, A.; Raciti, S. M.; Budney, J.; Hutyra, L.; Floerchinger, C. R.; Herndon, S. C.; Nehrkorn, T.; Zahniser, M. S.; Sargent, M. R.; Jackson, R. B.; Phillips, N. G.; Wofsy, S. C.

2015-12-01

Methane emissions from the natural gas supply-chain are highly uncertain and can vary widely among components and processes. We present an atmosphere-based method for detecting and quantifying the area and time-averaged surface flux of methane from natural gas infrastructure, and its application to the case-study of Boston, Massachusetts. Continuous measurements of atmospheric methane at a network of stations, inside and outside the city, are used to quantify the atmospheric methane gradient due to emissions from the urban area. Simultaneous observations of atmospheric ethane, and data on the ethane and methane content of the pipeline gas flowing through the region, are used to trace the atmospheric methane enhancement to the natural gas source. An atmospheric transport model is used to quantitatively relate the observed methane enhancement to a surface flux from the whole urban region. We find that methane emissions from natural gas in the urban region over one year was equal to 2.7 ± 0.6 % of the natural gas delivered to the region. Our findings for Boston suggest natural-gas-consuming regions, generally, may be larger sources of methane to the atmosphere than is current estimated and represent areas of significant resource loss.

Ground truthing for methane hotspots at Railroad Valley, NV - application to Mars

Science.gov (United States)

Detweiler, A. M.; Kelley, C. A.; Bebout, B.; McKay, C. P.; DeMarines, J.; Yates, E. L.; Iraci, L. T.

2011-12-01

During the 2010 Greenhouse gas Observing SATellite (GOSAT) calibration and validation campaign at Railroad Valley (RRV) playa, NV, unexpected methane and carbon dioxide fluctuations were observed at the dry lakebed. Possible sources included the presence of natural gas (thermogenic methane) from oil deposits in the surrounding playa, and/or methane production from microbial activity (biogenic) in the subsurface of the playa. In the summer of 2011, measurements were undertaken to identify potential methane sources at RRV. The biogenicity of the methane was determined based on δ13C values and methane/ethane ratios. Soil gas samples and sediments were collected at different sites in the playa and surrounding areas. The soils of the playa consist of a surface crust layer (upper ~ 10 cm) grading to a dense clay below about 25 cm. Soil gas from the playa, sampled at about 20 and 80 cm depths, reflected atmospheric methane concentrations, ranging from 2 to 2.4 ppm, suggesting that no methane was produced within the playa. Natural springs on the northeast and western border of the playa, detected as methane hotspots from a flyover by the Sensor Integrated Environmental Remote Research Aircraft (SIERRA), were also sampled. Bubbles in these springs had methane concentrations that ranged from 69 to 84% by volume. In addition, ethane was detected at very low concentrations, giving methane/ethane ratios in excess of 100,000, indicating biogenic methane in the springs. Soils and sediments collected at the playa and spring sites were incubated in vials over a period of ~23 days. Methane production was observed in the spring sites (avg. 228.6 ± 49.1 nmol/g/d at Kate Springs), but was not evident for the playa sites. The incubation data, therefore, corroborated in situ methane concentration measurements. Particulate organic carbon (POC) was low for all sites samples (0.05-0.38%), with the exception of Kate Springs, which had a much higher POC concentration of 3.4 ± 0

Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

Science.gov (United States)

Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

2015-12-14

The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ethane selective IRMOF-8 and its significance in ethane-ethylene separation by adsorption.

Science.gov (United States)

Pires, João; Pinto, Moisés L; Saini, Vipin K

2014-08-13

The separation of ethylene from ethane is one of the most energy-intensive single distillations practiced. This separation could be alternatively made by an adsorption process if the adsorbent would preferentially adsorb ethane over ethylene. Materials that exhibit this feature are scarce. Here, we report the case of a metal-organic framework, the IRMOF-8, for which the adsorption isotherms of ethane and ethylene were measured at 298 and 318 K up to pressures of 1000 kPa. Separation of ethane/ethylene mixtures was achieved in flow experiments using a IRMOF-8 filled column. The interaction of gas molecules with the surface of IRMOF-8 was explored using density functional theory (DFT) methods. We show both experimentally and computationally that, as a result of the difference in the interaction energies of ethane and ethylene in IRMOF-8, this material presents the preferential adsorption of ethane over ethylene. The results obtained in this study suggest that MOFs with ligands exhibiting high aromaticity character are prone to adsorb ethane preferably over ethylene.

Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

Science.gov (United States)

Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

2014-12-01

Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

Science.gov (United States)

Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

2006-01-11

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively

Ethane supply and demand

International Nuclear Information System (INIS)

Jamerson, J.B.

1993-01-01

Estimates are given for ethane production, chiefly from the Gulf Coast area. Increase in interregional transfers are predicted. Comparisons from 1992 through 1995 are made. The author concludes the following: ethane will be supply limited over the decade of the 90's; values will be over competing feedstocks; minimum practical demands will be close to available supply; regional relationships will reflect pipeline tariffs; purity ethane/EP spreads may narrow with new Mt. Belvieu fractionation capacity; new domestic supplies will back out imports; and Ethane's share of ethylene production may drop over the period

Renegotiating ethane contracts from producer/processor perspectives

International Nuclear Information System (INIS)

Hawkins, D. J.

1997-01-01

An overview of commercial practices relating to ethane sup ply and other collateral issues, including the variety of technologies used in the recovery of ethane and the manufacture of ethylene was provided. Ethane supply and demand balances, the Alberta ethane supply, the justifications for ethane recovery, the need for renegotiating ethane contracts in view of the changing Alberta market, the major price components , producers and processors' objectives in ethane sales, the nature of ethane contracts, and ethane pricing mechanisms were reviewed. The 'Alberta Advantage' based on gas price, large-scale ethane recovery, proximity to the largest market in the world, efficient transportation and fractionation facilities, further enhanced by deregulation and reduced regulatory barriers, was described. It was suggested that the enhanced competition and increase in market diversity demands a transparency in pricing that may well be realized as additional players enter the petrochemical business, and as competing transportation, processing and fractionation options become available to ethane suppliers and purchasers.1 tab

LLNL Chemical Kinetics Modeling Group

Energy Technology Data Exchange (ETDEWEB)

Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

2008-09-24

The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

Global impacts of tropospheric halogens (Cl, Br, I on oxidants and composition in GEOS-Chem

Directory of Open Access Journals (Sweden)

T. Sherwen

2016-09-01

Full Text Available We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I. Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016 we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3 concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 % due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 % but Cl oxidation of other VOCs (ethane, acetone, and propane can be significant (∼  15–27 %. Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts.

Science.gov (United States)

McKain, Kathryn; Down, Adrian; Raciti, Steve M; Budney, John; Hutyra, Lucy R; Floerchinger, Cody; Herndon, Scott C; Nehrkorn, Thomas; Zahniser, Mark S; Jackson, Robert B; Phillips, Nathan; Wofsy, Steven C

2015-02-17

Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4 ⋅ m(-2) ⋅ y(-1). Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼ 60-100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

Autoignited laminar lifted flames of methane, ethylene, ethane, and n-butane jets in coflow air with elevated temperature

KAUST Repository

Choi, Byungchul

2010-12-01

The autoignition characteristics of laminar lifted flames of methane, ethylene, ethane, and n-butane fuels have been investigated experimentally in coflow air with elevated temperature over 800. K. The lifted flames were categorized into three regimes depending on the initial temperature and fuel mole fraction: (1) non-autoignited lifted flame, (2) autoignited lifted flame with tribrachial (or triple) edge, and (3) autoignited lifted flame with mild combustion. For the non-autoignited lifted flames at relatively low temperature, the existence of lifted flame depended on the Schmidt number of fuel, such that only the fuels with Sc > 1 exhibited stationary lifted flames. The balance mechanism between the propagation speed of tribrachial flame and local flow velocity stabilized the lifted flames. At relatively high initial temperatures, either autoignited lifted flames having tribrachial edge or autoignited lifted flames with mild combustion existed regardless of the Schmidt number of fuel. The adiabatic ignition delay time played a crucial role for the stabilization of autoignited flames. Especially, heat loss during the ignition process should be accounted for, such that the characteristic convection time, defined by the autoignition height divided by jet velocity was correlated well with the square of the adiabatic ignition delay time for the critical autoignition conditions. The liftoff height was also correlated well with the square of the adiabatic ignition delay time. © 2010 The Combustion Institute.

Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

Science.gov (United States)

Thompson, Matthew G K; Parnis, J Mark

2005-10-27

The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.

Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

International Nuclear Information System (INIS)

Rey, M.D.; Font, R.; Aracil, I.

2013-01-01

An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm 3 which is below the limit of 150 mg/Nm 3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines

Retrievals of ethane from ground-based high-resolution FTIR solar observations with updated line parameters: determination of the optimum strategy for the Jungfraujoch station.

Science.gov (United States)

Bader, W.; Perrin, A.; Jacquemart, D.; Sudo, K.; Yashiro, H.; Gauss, M.; Demoulin, P.; Servais, C.; Mahieu, E.

2012-04-01

Ethane (C2H6) is the most abundant Non-Methane HydroCarbon (NMHC) in the Earth's atmosphere, with a lifetime of approximately 2 months. C2H6 has both anthropogenic and natural emission sources such as biomass burning, natural gas loss and biofuel consumption. Oxidation by the hydroxyl radical is by far the major C2H6 sink as the seasonally changing OH concentration controls the strong modulation of the ethane abundance throughout the year. Ethane lowers Cl atom concentrations in the lower stratosphere and is a major source of peroxyacetyl nitrate (PAN) and carbon monoxide (by reaction with OH). Involved in the formation of tropospheric ozone and in the destruction of atmospheric methane through changes in OH, C2H6 is a non-direct greenhouse gas with a net-global warming potential (100-yr horizon) of 5.5. The retrieval of ethane from ground-based infrared (IR) spectra is challenging. Indeed, the fitting of the ethane features is complicated by numerous interferences by strong water vapor, ozone and methane absorptions. Moreover, ethane has a complicated spectrum with many interacting vibrational modes and the current state of ethane parameters in HITRAN (e.g. : Rothman et al., 2009, see http://www.hitran.com) was rather unsatisfactory in the 3 μm region. In fact, PQ branches outside the 2973-3001 cm-1 range are not included in HITRAN, and most P and R structures are missing. New ethane absorption cross sections recorded at the Molecular Spectroscopy Facility of the Rutherford Appleton Laboratory (Harrison et al., 2010) are used in our retrievals. They were calibrated in intensity by using reference low-resolution spectra from the Pacific Northwest National Laboratory (PNNL) IR database. Pseudoline parameters fitted to these ethane spectra have been combined with HITRAN 2004 line parameters (including all the 2006 updates) for all other species encompassed in the selected microwindows. Also, the improvement brought by the update of the line positions and intensities

Solid–liquid equilibria for binary and ternary systems with the Cubic-Plus-Association (CPA) equation of state

DEFF Research Database (Denmark)

Fettouhi, André; Thomsen, Kaj

2010-01-01

A systematic investigation of the CPA model's performance within solid-liquid equilibria (SLE) in binary mixtures (methane + ethane, methane + heptane, methane + benzene, methane + CO2, ethane + heptane, ethane + CO2, 1-propanol + 1,4-dioxane, ethanol + water, 2-propanol + water) is presented. Th....... The results from the binary mixtures are used to predict SLE behaviour in ternary mixtures (methane + ethane + heptane, methane + ethane + CO2). Our results are compared with experimental data found in the literature....

A mechanistic study on the oxidative coupling of methane over lithium doped magnesium oxide catalysts

NARCIS (Netherlands)

Geerts, J.W.M.H.; Kasteren, van J.M.N.; Wiele, van der K.; Imarisio, G.; Frias, M.; Berntgen, J.M.

1988-01-01

To elucidate the importance of various reaction steps in the oxidative convers ion of methane, experiments were carried out with three reaction products: ethane, ethylene and carbon monoxide. These products were studied seperately, in oxidation experiments with and without a catalyst. Moreover , the

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

Science.gov (United States)

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Halogenated fatty acids

DEFF Research Database (Denmark)

Mu, Huiling; Sundin, Peter; Wesén, Clas

1997-01-01

Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation......), atomic emission spectrometry, and mass spectrometry. For most environmental samples, chlorinated FAMEs must be enriched prior to GC. ELCD is a useful detection method for indicating halogenated FAMEs in the chromatograms, and tentative identification of the halogenated species can be obtained...

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

Science.gov (United States)

Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

2015-05-06

The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

Aging tests of ethylene contaminated argon/ethane

International Nuclear Information System (INIS)

Atac, M.; Bauer, G.

1994-01-01

We report on aging tests of argon/ethane gas with a minor (1800 ppM) component of ethylene. The measurements were first conducted with the addition of alcohol to test the suppression of aging by this additive, with exposure up to ∼1.5 C/cm. Tests have included: a proportional tube with ethanol, another with isopropyl alcohol, and for comparison a tube has also been run with ethanol and argon/ethane from CDF's old (ethylene-free) ethane supply. The aging test with ethanol showed no difference between the ethylene-free and the ethylene tube. Furthermore, raw aging rates of argon/ethane and argon/ethane/ethylene were measured by exposing tubes without the addition of alcohol to about 0.1 C/cm. Again, no significant difference was observed. In conclusion, we see no evidence that ethylene contamination up to 1800 ppM has any adverse effect on wire aging. However, this level of ethylene does seem to significantly suppress the gas gain

Detection of abundant ethane and methane, along with carbon monoxide and water, in comet C/1996 B2 Hyakutake: evidence for interstellar origin

Science.gov (United States)

Mumma, M. J.; DiSanti, M. A.; Dello Russo, N.; Fomenkova, M.; Magee-Sauer, K.; Kaminski, C. D.; Xie, D. X.

1996-01-01

The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.

On surface reactions of iron tungstate with ethane

International Nuclear Information System (INIS)

Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

1980-01-01

Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

Analysis of Non-Methane Hydrocarbon Data from 2004-2016 in a Subtropical Area close to the Gulf of Mexico

Science.gov (United States)

Rappenglueck, B.

2017-12-01

Speciated C2-C11 non-methane hydrocarbons (NMHC) have been measured online on an hourly basis at Lake Jackson/TX close to the Gulf of Mexico. Altogether 48 NMHCs along with NO, NO2, NOx, O3 have been collected continuously from January 2004-December 2016 under the auspices of the Texas Commission on Environmental Quality. Data was screened for background conditions representing marine wind sectors. The data set represents a combination of marine air masses mixed with local biogenic emissions. The data analysis addresses photochemical processing of air masses as reflected in the relationship of ln(n-butane/ethane) vs. ln(propane/ethane) and ln(i-butane/ethane) vs. ln(n-butane/ethane). In addition, key NMHC relationships for radical chemistry, e.g. i-butane vs n-butane for OH and Cl chemistry and i-pentane vs. n-pentane for NO3 chemistry, are discussed. Seasonal analysis revealed a clear trend with maximum NMHC mixing ratios in winter time and lowest mixing ratios in summer reflecting the impact of photochemical processes in summer. Propene equivalents were highest during summertime, with significant contributions from alkenes, including isoprene. The relation of propane/ethane vs ethane indicates seasonal variation with lowest values (i.e. most aged air masses) in winter.

Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

Science.gov (United States)

Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

2016-05-15

This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluating ethane and methane emissions associated with the development of oil and natural gas extraction in North America

Science.gov (United States)

Franco, B.; Mahieu, E.; Emmons, L. K.; Tzompa-Sosa, Z. A.; Fischer, E. V.; Sudo, K.; Bovy, B.; Conway, S.; Griffin, D.; Hannigan, J. W.; Strong, K.; Walker, K. A.

2016-04-01

Sharp rises in the atmospheric abundance of ethane (C2H6) have been detected from 2009 onwards in the Northern Hemisphere as a result of the unprecedented growth in the exploitation of shale gas and tight oil reservoirs in North America. Using time series of C2H6 total columns derived from ground-based Fourier transform infrared (FTIR) observations made at five selected Network for the Detection of Atmospheric Composition Change sites, we characterize the recent C2H6 evolution and determine growth rates of ˜5% yr-1 at mid-latitudes and of ˜3% yr-1 at remote sites. Results from CAM-chem simulations with the Hemispheric Transport of Air Pollutants, Phase II bottom-up inventory for anthropogenic emissions are found to greatly underestimate the current C2H6 abundances. Doubling global emissions is required to reconcile the simulations and the observations prior to 2009. We further estimate that North American anthropogenic C2H6 emissions have increased from 1.6 Tg yr-1 in 2008 to 2.8 Tg yr-1 in 2014, i.e. by 75% over these six years. We also completed a second simulation with new top-down emissions of C2H6 from North American oil and gas activities, biofuel consumption and biomass burning, inferred from space-borne observations of methane (CH4) from Greenhouse Gases Observing SATellite. In this simulation, GEOS-Chem is able to reproduce FTIR measurements at the mid-latitudinal sites, underscoring the impact of the North American oil and gas development on the current C2H6 abundance. Finally we estimate that the North American oil and gas emissions of CH4, a major greenhouse gas, grew from 20 to 35 Tg yr-1 over the period 2008-2014, in association with the recent C2H6 rise.

Apparatus for washing out halogens

Energy Technology Data Exchange (ETDEWEB)

Pier, M; Hahn, J; Kroenig, W

1941-03-26

An apparatus is described for washing out of halogens and the like or liquid halogen compounds from the products, which are formed on pressure hydrogenation or splitting of carbon-containing material in the presence of halogens or halogen compounds, consisting of a washing apparatus installed between the reaction vessel and the hot separator, which is inclined in relatively small space for steam regulation and contains, with the steam, arranged baffles, especially spirals.

Membrane-based ethylene/ethane separation: The upper bound and beyond

KAUST Repository

Rungta, Meha

2013-08-02

Ethylene/ethane separation via cryogenic distillation is extremely energy-intensive, and membrane separation may provide an attractive alternative. In this paper, ethylene/ethane separation performance using polymeric membranes is summarized, and an experimental ethylene/ethane polymeric upper bound based on literature data is presented. A theoretical prediction of the ethylene/ethane upper bound is also presented, and shows good agreement with the experimental upper bound. Further, two ways to overcome the ethylene/ethane upper bound, based on increasing the sorption or diffusion selectivity, is also discussed, and a review on advanced membrane types such as facilitated transport membranes, zeolite and metal organic framework based membranes, and carbon molecular sieve membranes is presented. Of these, carbon membranes have shown the potential to surpass the polymeric ethylene/ethane upper bound performance. Furthermore, a convenient, potentially scalable method for tailoring the performance of carbon membranes for ethylene/ethane separation based on tuning the pyrolysis conditions has also been demonstrated. © 2013 American Institute of Chemical Engineers.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

Science.gov (United States)

Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

2011-05-01

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

40 CFR 721.3248 - Ethane, 1,2,2- trichlorodifluoro-.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 1,2,2- trichlorodifluoro-. 721... Substances § 721.3248 Ethane, 1,2,2- trichlorodifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 1,2,2-trichlorodifluoro- (CAS No...

Studies on the pore water sulfate, chloride and sedimentary methane to understand the sulfate reduction process in the eastern Arabian Sea

Digital Repository Service at National Institute of Oceanography (India)

Karisiddaiah, S.M.; Borole, D.V.; Rao, B.R.; Paropkari, A.L.; Joao, H; Kocherla, M.; Sarkar, G.P.; Biswas, G.; Kumar, N.

Sediment cores (~5 m length) from ten stations collected in the water depths of 2665-3210 m in the eastern Arabian Sea were studied for pore water sulfate (SO42-), chloride (Cl-) and lighter-hydrocarbons (methane: C1, ethane:C2 and propane: C3...

Irradiation of Methane by Recoiling Fission-Fragments

Energy Technology Data Exchange (ETDEWEB)

Hall, G. R.; Galley, M. R. [Imperial College of Science and Technology, London (United Kingdom)

1963-11-15

Pure methane gas (containing <0.003% oxygen and <5 mg H{sub 2}O per m{sup 3}) has been irradiated at pressures ranging from 5 to 50 atmospheres pressure and at 30{sup o}C with recoiling fission - fragments. The gas is contained in a silica ampoule of volume about 9 cm{sup 3} and which also contains a platinum cylinder coated on the inside with 0.5 mg/cm{sup 2} highly enriched uranium oxide. When the ampoule is irradiated in a nuclear reactor with thermal neutrons, about half the fission-fragments recoil from the uranium and dissipate their energy in the methane. In a typical irradiation, methane at 10 atm pressure receives a dose of 5 x 10{sup 21} eV at an integrated reactor flux of 5 x 10{sup 15} neutrons/cm{sup 2}. Neutron flux i s measured by means of a gold-foil flux monitor. The activity of the Au{sup 198} is counted in a 4 {pi} proportional counter. The irradiation products have been detected by using beta-ionization detectors for gas-phase chromatography with suitable columns. The following products have been found: hydrogen, ethane, propane, n-butane, isobutane, n-pentane, iso-pentane, neo-pentane, the seven hexanes. Traces of higher hydrocarbons are undoubtedly present but the analysis of these has not been attempted. Hydrogen is present in greatest yield and the yields of the hydrocarbons decrease in the order given above. Despite previously reported yields of ethylene (G-value-0.1) from gamma and fast - electron irradiations, no ethylene or other unsaturated products have been detected in this work. It would have been possible to detect 10 ppm in the products. This is to be expected as any double bonds which may be produced would almost immediately be hydrogenated by the hydrogen present. Yields for hydrogen, ethane and propane lie within the range of values that have been reported by other workers for gamma and fast electron irradiations. (author)

Emission spectra of gaseous avalanches and their time structure

International Nuclear Information System (INIS)

Fraga, M.M.; Lima, E.P. de; Marques, R.F.; Policarpo, A.J.P.L.; Alves, M.A.F.; Salete, M.; Leite, S.C.P.

1993-01-01

Following previous measurements in argon/methane mixtures, the authors now report on the emission spectra of argon/ethane and methane/ethane mixtures, in the region from 120 to 450 nm, for a single wire chamber working in the proportional and/or self-quenching streamer modes. Identification of radicals and fragments is attempted. The time evolution of VUV light, relevant to photon feedback processes, is presented for the CI lines at 156.1 and 165.7nm in argon/methane, argon/ethane and methane/ethane mixtures

Quantum molecular dynamics simulations of thermophysical properties of fluid ethane.

Science.gov (United States)

Zhang, Yujuan; Wang, Cong; Zheng, Fawei; Zhang, Ping

2012-12-01

We have performed first-principles molecular-dynamics simulations based on density-functional theory to study the thermophysical properties of ethane under extreme conditions. We present results for the equation of state of fluid ethane in the warm dense region. The optical conductivity is calculated via the Kubo-Greenwood formula from which the dc conductivity and optical reflectivity are derived. The close correlation between the nonmetal-metal transition of ethane and its decomposition, that ethane dissociates significantly into molecular and/or atomic hydrogen and some long alkane chains, has been systematically studied by analyzing the optical conductivity spectra, pair correlation functions, electronic density of states, and charge density distribution of fluid ethane.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1978--February 14, 1979

International Nuclear Information System (INIS)

Rack, E.P.

1979-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, were studied in gaseous, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes and other organic systems in order to better understand the mechanisms and dynamics of high energy monovalent species. The experimental and theoretical program consists of six interrelated areas: (1) the reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure and liquid systems; (2) the gas to condensed state transition in halogen high chemistry, involving bromine activated by the (n,γ) and (I.T.) processes in ethane was investigated in more detail; (3) systematics of halogen hot atom reactions. The reactions of 80 Br/sup m/, 80 Br, 82 Br/sup m/ + 82 Br, 82 Br, 128 I, 130 I, and 130 I/sup m/ + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators; (4) kinetic theory applications of high energy reactions and mathematical development of caging mechanisms were developed; (5) the sterochemistry of 38 Cl substitution reactions involving diastereomeric 1,2-dichloro-1,2-difluorethane in liquid mixtures was completed, suggesting that the stereochemical course of the substitution process is controlled by the properties of the solvent molecules; and (6) the applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems was continued, especially involving aluminum and vanadium trace determinations

Ethane-xenon mixtures under shock conditions

Science.gov (United States)

Flicker, Dawn; Magyar, Rudolph; Root, Seth; Cochrane, Kyle; Mattsson, Thomas

2015-06-01

Mixtures of light and heavy elements arise in inertial confinement fusion and planetary science. We present results on the physics of molecular scale mixing through a validation study of equation of state (EOS) properties. Density functional theory molecular dynamics (DFT/QMD) at elevated-temperature and pressure is used to obtain the properties of pure xenon, ethane, and various compressed mixture compositions along their principal Hugoniots. To validate the QMD simulations, we performed high-precision shock compression experiments using Sandia's Z-Machine. A bond tracking analysis of the simulations correlates the sharp rise in the Hugoniot curve with completion of dissociation in ethane. DFT-based simulation results compare well with experimental data and are used to provide insight into the dissociation as a function of mixture composition. Interestingly, we find that the compression ratio for complete dissociation is similar for ethane, Xe-ethane, polymethyl-pentene, and polystyrene, suggesting that a limiting compression exists for C-C bonded systems. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, Security Administration under contract DE-AC04-94AL85000.

Atmospheric chemistry of ethane and ethylene

International Nuclear Information System (INIS)

Aikin, A.C.; Herman, J.R.; Maier, E.J.; McQuillian, C.J.

1982-01-01

A detailed study of ethane and ethylene photochemistry is presented for the troposphere and stratosphere. It is demonstrated that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Observation of ethane show a stratospheric behavior indicative of a free chlorine concentration below 30 km that is only 10% of the predicted value given by both our photochemical model calculations and those done by others. The inferred lower amount of chlorine cannot be explained by heterogeneous processes for concentration of aerosols representing average background conditions, nor does current stratospheric photochemistry show agreement. Chemical destruction of ethane and ethylene within the atmosphere leads to the production of carbon monoxide, formaldehyde, and other products. Tropospheric concentrations of formaldehyde are enhanced by nearly a factor of 3 for an ethylene mixing ratio of 2 ppb. Simultaneous monitoring of formaldehyde and carbon monoxide, as well as other products, will greatly aid in determining the relative importance of different tropospheric CO sources. Peroxyacetyl nitrate (PAN) acts as a reservoir for odd-nitrogen at the expense of HNO 3 HO 2 NO 2 , NO, and NO 2

Supply of ethane and transportation to the petrochemical industry

International Nuclear Information System (INIS)

Moe, D.

1997-01-01

This presentation reviewed the existing infrastructure for ethane delivery and distribution from Alberta and assessed future potential. Large investments continue to be made to expand pipelines and petrochemical plants, at the same time, the sufficiency of ethane supplies for all projects to proceed are being questioned. Some current projects such as the Empress to Kerrobert pipeline expansion, the NCL Straddle Plant at Taylor, the PacRim LNG project, the new fractionation plant at Fort Saskatchewan, the Alliance Pipeline project to connect gas and ethane, and the impact of Alliance and PacRim on available ethane were reviewed. The competition for supplies is increasing and the export of ethane is expected to continue at low levels. Recent regulatory decisions about producers rights and upcoming challenges (NOVA load retention tolling, component balancing on NOVA, competitive hearings) were also outlined. 9 figs

Recent increase of ethane detected in the remote atmosphere of the Northern Hemisphere

Science.gov (United States)

Franco, Bruno; Bader, Whitney; Bovy, Benoît; Mahieu, Emmanuel; Fischer, Emily V.; Strong, Kimberly; Conway, Stephanie; Hannigan, James W.; Nussbaumer, Eric; Bernath, Peter F.; Boone, Chris D.; Walker, Kaley A.

2015-04-01

Ethane (C2H6) has a large impact on tropospheric composition and air quality because of its involvement in the global VOC (volatile organic compound) - HOx - NOx chemistry responsible for generating and destroying tropospheric ozone. By acting as a major sink for tropospheric OH radicals, the abundance of C2H6 influences the atmospheric content of carbon monoxide and impacts the lifetime of methane. Moreover, it is an important source of PAN, a thermally unstable reservoir for NOx radicals. On a global scale, the main sources of C2H6 are leakage from the production, transport of natural gas loss, biofuel consumption and biomass burning, mainly located in the Northern Hemisphere. Due to its relatively long lifetime of approximately two months, C2H6 is a sensitive indicator of tropospheric pollution and transport. Using an optimized retrieval strategy (see Franco et al., 2014), we present here a 20-year long-term time series of C2H6 column abundance retrieved from ground-based Fourier Transform InfraRed (FTIR) solar spectra recorded from 1994 onwards at the high-altitude station of Jungfraujoch (Swiss Alps, 46.5° N, 3580 m a.s.l.), part of the Network for the Detection of Atmospheric Composition Change (NDACC, see http://www.ndacc.org). After a regular 1994 - 2008 decrease of the C2H6 amounts, which is very consistent with prior major studies (e.g., Aydin et al., 2011; Simpson et al., 2012) and our understanding of global C2H6 emissions, trend analysis using a bootstrap resampling tool reveals a C2H6 upturn and a statistically-significant sharp burden increase from 2009 onwards (Franco et al., 2014). We hypothesize that this observed recent increase in C2H6 could affect the whole Northern Hemisphere and may be related to the recent massive growth in the exploitation of shale gas and tight oil reservoirs. This hypothesis is supported by measurements derived from solar occultation observations performed since 2004 by the Atmospheric Chemistry Experiment - Fourier

Halogenated arsenenes as Dirac materials

International Nuclear Information System (INIS)

Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

2016-01-01

Highlights: • We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. • All fully-halogenated arsenene except As_2I_2 would spontaneously form and stable in defending the thermal fluctuation in room temperature. - Abstract: Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155–3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

Metabolism of inhaled ethane and pentane by the intact rat

International Nuclear Information System (INIS)

Daugherty, M.S.; Luddent, T.M.; Burk, R.F.

1986-01-01

Measurement of exhaled ethane or pentane is a noninvasive technique for studying in vivo lipid peroxidation. Many past studies have assumed that pentane and ethane are not metabolized. Radiolabeled ( 14 C) ethane and pentane were used to study the disposition of these compounds in intact rats. Rats were placed for 8 h in a closed plexiglass chamber fitted with a system for replenishing chamber atmospheric O 2 . Evolved CO 2 was trapped by recirculating chamber air through 3 N NaOH contained in a vessel external to the chamber. Radiolabeled ethane or pentane was injected into the chamber at the start of each experiment. The percent of 14 C-activity added to the chamber recovered in the CO 2 trap, urine, and chamber air at the end of the experiment (8 h) in the [ 14 C]-ethane (n=5) and [ 14 C]-pentane (n=4) studies are presented. Results indicate that both ethane and pentane are metabolized to CO 2 in the intact rat. Possible changes in ethane and pentane metabolism must be considered if the exhalation rates of these hydrocarbons are to be used as indices of in vivo lipid peroxidation

Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

Science.gov (United States)

Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

2016-11-23

The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

Variability of ethane on Jupiter

Science.gov (United States)

Kostiuk, Theodor; Espenak, Fred; Mumma, Michael J.; Deming, Drake; Zipoy, David

1987-01-01

Varying stratospheric temperature profiles and C2H6 altitude distributions furnish contexts for the evaluation of ethane abundances and distributions in the Jupiter stratosphere. Substantial ethane line emission and retrieved mole fraction variability is noted near the footprint of Io's flux tube, as well as within the auroral regions. It is suggested that this and other observed phenomena are due to the modification of local stratospheric chemistry by higher-order effects, which are in turn speculated to be due to the precipitation of charged particles along magnetic field lines.

Ethane abundance on Neptune

Science.gov (United States)

Kostiuk, Theodor; Espenak, Fred; Romani, Paul; Zipoy, David; Goldstein, Jeff

1990-01-01

IR spectroscopic measurements of the C2H6 RR (4,5) emission line at 840.9764/cm have been used to infer Neptune's ethane mole fractions; while the resulting value is lower than that obtained by Orton et al. (1987), it lies within their 2-sigma error bounds. The present results are also found to require 2.0-5.8 times more ethane in the 0.02-2 mbar pressure region than predicted by the Romani and Atreya (1989) photochemical model. Better agreement is obtainable through a reduction of eddy mixing in the lower stratosphere and/or an increase of stratospheric temperature by more than 10 K above the 6-mbar level.

Production of radiohalogens and [11C]-methane at high specific activity

Science.gov (United States)

Nye, Jonathon Andrew

2005-07-01

The halogens, occupying Group VII of the periodic table, play an important role in the biochemical processes underlying health and disease. A variety of positron emitters covering a broad range of half-lives permit the imaging of the body's physiochemical behavior using PET. Neutron deficient isotopes of the halogen group can be produced by (p,n) reactions from enriched targets with low energy (production process insures their role in the clinical/research environment, labeling H215 O, 13NH3, CH3-compounds and 18F-FDG. Halogens with half-lives longer than 18F have been avoided due to a combination of several factors, such as complexity of the target systems, expense of the enriched substrate, low reaction yields, and extensive post-processing to reclaim the target material. PET research over the last decade has forced a match between drug development and emerging small animal instrumentation, shifting focus to agents labeled with high specific activity 11CH3I and the long-lived radiohalogens, 76Br and 124I. A steady local supply of 18F-fluoride, 11C-methane, 76B-bromide, and 124I-iodide is essential to seize today's research opportunities or for limited distribution outside of our local area. To keep pace, new targetry developments are implemented to reliably produce these isotopes on a batch basis. The research presented details improvements on existing production methods for 18F-fluoride intended for nucleophilic substitution and high specific activity 11C-methane (→CH3I) for the N-methylation of a half-dozen neuroligands. A significant effort is placed on the novel use of low energy cyclotrons for the production of 76Br and 124I involved in labeling antibody and protein agents. Performance of these new designs and the success of the solid targetry development will be described. The ten-fold scale-up in yields at end-of-bombardment promises new hope for the synthesis of PET tracers, previously limited by access to the radio-halogen precursors.

First experience with the new solid methane moderator at the IBR-2 reactor

International Nuclear Information System (INIS)

Beliakov, A.A.; Shabalin, E.P.; Tretyakov, I.T.

2001-01-01

In the 1999 Fall the solid methane moderator (CM) has been installed and tested at full power at the IBR-2 pulsed reactor. Its main features are a beryllium reflector and a light water premoderator. Radiation load on the methane was three times as much as that of IPNS facility, namely, 0.1 W/g. Effects of temperature, operation time, concentration of a hydrogen scavenger, and annealing procedure on both neutron and service performances were studied. Maximum operation time of a newly loaded portion of methane was 4 days. In this time around 30% of methane is transformed into hydrogen, ethane, and high molecular hydrocarbons, and yet no deterioration in cold neutron intensity was detected. Among new knowledge, the most important are two facts observed: two-fold decrease in hydrogen formation rate when methane is poisoned with 2.5% to 5% of ethylene, and low formation rate of solid, inremovable products of radiolysis - (1.5/3)10 -7 g/J, which means that after 10 years of operation the methane chamber will be filled with only 100 g of residue. Gain of factor 20 in cold neutron flux was obtained as compared to the routine grooved light water moderator. Presently, it is the highest among the intense pulsed neutron sources. (author)

Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania.

Science.gov (United States)

Kang, Mary; Kanno, Cynthia M; Reid, Matthew C; Zhang, Xin; Mauzerall, Denise L; Celia, Michael A; Chen, Yuheng; Onstott, Tullis C

2014-12-23

Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells ("controls") in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10(-6) kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10(-3) kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4-7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories.

In Situ Bioremediation of 1,4-Dioxane by Methane Oxidizing Bacteria in Coupled Anaerobic-Aerobic Zones

Science.gov (United States)

2016-02-11

FINAL REPORT In Situ Bioremediation of 1,4-Dioxane by Methane Oxidizing Bacteria in Coupled Anaerobic-Aerobic Zones SERDP Project ER-2306...volatile organic compound (CVOCs), ethene and ethane in groundwater at Raritan Arsenal Area 18C after in situ bioremediation . 4 List of...aquifers, the bioremediation approach most commonly used for chlorinated solvents. The ability of methanotrophs to biodegrade 1,4-dioxane was

Ethane and acetylene abundances in the Jovian atmosphere

Science.gov (United States)

Tokunaga, A.; Knacke, R. F.; Owen, T.

1976-01-01

The paper reports spectra of Jupiter in the spectral region from 755 to 850 kaysers, which covers the nu-9 fundamental of ethane and contains lines from the R branch of the nu-5 fundamental of acetylene. The monochromatic absorption coefficient of the central Q branch of the nu-9 fundamental of ethane, which was determined in the laboratory, is applied in a radiative-transfer calculation to evaluate the ethane mixing ratio in the Jovian atmosphere; the present data are also used to place an upper limit on the acetylene mixing ratio. For the radiative-transfer calculation, emission intensity is computed for the region above the 0.02-atm level assuming both an isothermal inversion layer and a previously reported temperature profile. The resulting maximum mixing ratios consistent with the observations are 0.00003 for ethane and 7.5 by 10 to the -8th power for acetylene.

High-pressure oxidation of ethane

DEFF Research Database (Denmark)

Hashemi, Hamid; G. Jacobsen, Jon; Rasmussen, Christian T.

2017-01-01

Ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending...... on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate...

Evidence for Interfacial Halogen Bonding.

Science.gov (United States)

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for the existence of supercooled ethane droplets under conditions prevalent in Titan's atmosphere.

Science.gov (United States)

Sigurbjörnsson, Omar F; Signorell, Ruth

2008-11-07

Recent evidence for ethane clouds and condensation in Titan's atmosphere raise the question whether liquid ethane condensation nuclei and supercooled liquid ethane droplets exist under the prevalent conditions. We present laboratory studies on the phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions relevant to Titan's atmosphere. Combining bath gas cooling with infrared spectroscopy, we find evidence for the existence of supercooled liquid ethane aerosol droplets. The observed homogeneous freezing rates imply that supercooled ethane could be a long-lived species in ethane-rich regions of Titan's atmosphere similar to supercooled water in the Earth's atmosphere.

Tropospheric Halogen Chemistry

Science.gov (United States)

von Glasow, R.; Crutzen, P. J.

2003-12-01

Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

Titan's Methane Cycle is Closed

Science.gov (United States)

Hofgartner, J. D.; Lunine, J. I.

2013-12-01

Doppler tracking of the Cassini spacecraft determined a polar moment of inertia for Titan of 0.34 (Iess et al., 2010, Science, 327, 1367). Assuming hydrostatic equilibrium, one interpretation is that Titan's silicate core is partially hydrated (Castillo-Rogez and Lunine, 2010, Geophys. Res. Lett., 37, L20205). These authors point out that for the core to have avoided complete thermal dehydration to the present day, at least 30% of the potassium content of Titan must have leached into an overlying water ocean by the end of the core overturn. We calculate that for probable ammonia compositions of Titan's ocean (compositions with greater than 1% ammonia by weight), that this amount of potassium leaching is achievable via the substitution of ammonium for potassium during the hydration epoch. Formation of a hydrous core early in Titan's history by serpentinization results in the loss of one hydrogen molecule for every hydrating water molecule. We calculate that complete serpentinization of Titan's core corresponds to the release of more than enough hydrogen to reconstitute all of the methane atoms photolyzed throughout Titan's history. Insertion of molecular hydrogen by double occupancy into crustal clathrates provides a storage medium and an opportunity for ethane to be converted back to methane slowly over time--potentially completing a cycle that extends the lifetime of methane in Titan's surface atmosphere system by factors of several to an order of magnitude over the photochemically-calculated lifetime.

Halogen bond: a long overlooked interaction.

Science.gov (United States)

Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

2015-01-01

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

Modification of encapsulation pressure of reverse micelles in liquid ethane.

Science.gov (United States)

Peterson, Ronald W; Nucci, Nathaniel V; Wand, A Joshua

2011-09-01

Encapsulation within reverse micelles dissolved in low viscosity fluids offers a potential solution to the slow tumbling problem presented by large soluble macromolecules to solution NMR spectroscopy. The reduction in effective macromolecular tumbling is directly dependent upon the viscosity of the solvent. Liquid ethane is of sufficiently low viscosity at pressures below 5000 psi to offer a significant advantage. Unfortunately, the viscosity of liquid ethane shows appreciable pressure dependence. Reverse micelle encapsulation in liquid ethane often requires significantly higher pressures, which obviates the potential advantages offered by liquid ethane over liquid propane. Addition of co-surfactants or co-solvents can be used to manipulate the minimum pressure required to obtain stable, well-behaved solutions of reverse micelles prepared in liquid ethane. A library of potential additives is examined and several candidates suitable for use with encapsulated proteins are described. Copyright © 2011 Elsevier Inc. All rights reserved.

Sensitivity of orthopositronium annihilation to density fluctuations in ethane gas

International Nuclear Information System (INIS)

Eftekhari, A.

1982-01-01

The annihilation rates of orthopositronium (o-Ps) and free positrons and positronium formation fractions have been measured in gaseous ethane at seven temperatures between 295 and 377 K for densities in the range 1.2-286 amagat. The pick off quenching rate of o-Ps is observed to vary with temperature at low densities of ethane. The observed behavior of the o-Ps annihilation rates with density and temperature is interpreted in terms of density fluctuations in ethane gas. A simple theoretical model is developed which explains the observed annihilation behavior reasonably well at those temperatures and densities where density fluctuations are small. The annihilation rates of flow-energy positrons indicate the formation of positron-ethane collision complexes and self-trapping of positrons in clusters of ethane molecules. The o-Ps yields appear to be independent of temperature and show a strong dependence on the density of the gas

40 CFR 721.10086 - Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 2-(difluoromethoxy)-1,1,1... Specific Chemical Substances § 721.10086 Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 2...

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

Science.gov (United States)

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Halogen bonding in solution: thermodynamics and applications.

Science.gov (United States)

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

Absolute molecular sieve separation of ethylene/ethane mixtures with silver zeolite A.

Science.gov (United States)

Aguado, Sonia; Bergeret, Gérard; Daniel, Cecile; Farrusseng, David

2012-09-12

Absolute ethylene/ethane separation is achieved by ethane exclusion on silver-exchanged zeolite A adsorbent. This molecular sieving type separation is attributed to the pore size of the adsorbent, which falls between ethylene and ethane kinetic diameters.

Chemical and physical factors which control the substitution reactions of direct fission-produced iodine with gaseous methane and the methyl halides

International Nuclear Information System (INIS)

Kikuchi, M.; Church, L.B.

1976-01-01

The factors controlling the hydrogen and halogen substitution reactions resulting from direct fission-produced iodine isotopes (*I) with gaseous methane and methyl halides were investigated. The chemical reaction probabilities, corrected for any secondary decomposition, were compared as a function of various chemical and physical parameters. These include carbon-halogen bond strength, halogen electronegativity, volume and cross sectional area of the substituted and neighboring atoms. On the basis of this analysis, it is concluded that *I-for-X (where X = H, F, Cl, Br and I) substitution reactions are controlled by the cross sectional area of the X atom. The *I-for-H substitution probability is reduced in proportion to the volume of X, suggesting that steric interference is the dominant factor influencing the reaction probability. (orig.) [de

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Institute of Scientific and Technical Information of China (English)

ZHANG Zhe; ZHAO Zhen; XU Chunming

2005-01-01

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

Anaerobic biodegradation of halogenated and nonhalogenated N-, s-, and o-heterocyclic compounds in aquifer slurries

Science.gov (United States)

Adrian, Neal R.; Suflita, Joseph M.

1994-01-01

The fate of several halogenated and nonhalogenated heterocyclic compounds in anoxic aquifer slurries was investigated Substrate depletion and methane formation were monitored in serum bottle incubations by HPLC and GC, respectively Pyridine, pyrimidine, thiophene, and furan were not mineralized following an 11-month incubation, but the corresponding carboxylated or oxygenated compounds were That is, >74% of the theoretically expected amount of methane was recovered from nicotinic acid, uracil, or 2-furoic acid Chlorinated derivatives, like 2 chloro- or 6-chloronicotinic acid, as well as 4 chloro- and 5-chlorouracil resisted mineralization However, 5-bromouracil was reductively dehalogenated to stoichiometric amounts of uracil, whereas 2-chloropyrimidine was metabolized to a more polar unidentified compound that resisted further anaerobic biodegradation Microorganisms acclimated to 5-bromouracil were unable to transform 4 chloro or 5 chlorouracil These findings illustrate how the structure of heterocyclic contaminants influences their susceptibility to anaerobic decay

10 CFR 221.11 - Natural gas and ethane.

Science.gov (United States)

2010-01-01

... 10 Energy 3 2010-01-01 2010-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

Quantum molecular dynamics simulations of thermophysical properties of fluid ethane

OpenAIRE

Zhang, Yujuan; Wang, Cong; Zheng, Fawei; Zhang, Ping

2012-01-01

We have performed first-principles molecular-dynamics simulations based on density-functional theory to study the thermophysical properties of ethane under extreme conditions. We present new results for the equation of state of fluid ethane in the warm dense region. The optical conductivity is calculated via the Kubo-Greenwood formula from which the dc conductivity and optical reflectivity are derived. The close correlation between the nonmetal-metal transition of ethane and its decomposition...

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

Directory of Open Access Journals (Sweden)

J. Ofner

2012-07-01

Full Text Available Reactive halogen species (RHS, such as X·, X₂ and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

Membrane-based ethylene/ethane separation: The upper bound and beyond

KAUST Repository

Rungta, Meha; Zhang, Chen; Koros, William J.; Xu, Liren

2013-01-01

Ethylene/ethane separation via cryogenic distillation is extremely energy-intensive, and membrane separation may provide an attractive alternative. In this paper, ethylene/ethane separation performance using polymeric membranes is summarized

Organic halogens in landfill leachates

DEFF Research Database (Denmark)

Grøn, C.; Christensen, J. B.; Jensen, Dorthe Lærke

2000-01-01

Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organi...

Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

KAUST Repository

Belmabkhout, Youssef; Mouttaki, Hasnaa; Eubank, Jarrod F.; Guillerm, Vincent; Eddaoudi, Mohamed

2014-01-01

Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1

Selective Adsorption of Ethane over Ethylene in PCN-245: Impacts of Interpenetrated Adsorbent.

Science.gov (United States)

Lv, Daofei; Shi, Renfeng; Chen, Yongwei; Wu, Ying; Wu, Houxiao; Xi, Hongxia; Xia, Qibin; Li, Zhong

2018-03-07

The separation of ethane from ethylene using cryogenic distillation is an energy-intensive process in the industry. With lower energetic consumption, the adsorption technology provides the opportunities for developing the industry with economic sustainability. We report an iron-based metal-organic framework PCN-245 with interpenetrated structures as an ethane-selective adsorbent for ethylene/ethane separation. The material maintains stability up to 625 K, even after exposure to 80% humid atmosphere for 20 days. Adsorptive separation experiments on PCN-245 at 100 kPa and 298 K indicated that ethane and ethylene uptakes of PCN-245 were 3.27 and 2.39 mmol, respectively, and the selectivity of ethane over ethylene was up to 1.9. Metropolis Monte Carlo calculations suggested that the interpenetrated structure of PCN-245 created greater interaction affinity for ethane than ethylene through the crossing organic linkers, which is consistent with the experimental results. This work highlights the potential application of adsorbents with the interpenetrated structure for ethane separation from ethylene.

The formation of ethane from carbon dioxide under cold plasma

International Nuclear Information System (INIS)

Zhang Xiuling; Zhang Lin; Dai Bin; Gong Weimin; Liu Changhou

2001-01-01

Pulsed-corona plasma has been used as a new method for ethane dehydrogenation at low temperature and normal pressure using carbon dioxide as an oxidant. The effect of carbon dioxide content in the feed, power input, and flow rate of the reactants on the ethane dehydrogenation has been investigated. The experimental results show that the conversion of ethane increases with the increasing in the amount of carbon dioxide in the feed. The yield of ethylene and acetylene decreases with the increasing in the yield of carbon monoxide, indicating that the increased carbon dioxide leads to the part of ethylene and acetylene being oxidized to carbon monoxide. Power input is primarily an electrical parameter in pulsed-corona plasma, which plays an important role in reactant conversion and product formation. When the power input reaches 16 W, ethane conversion is 41.0% and carbon dioxide conversion is 26.3%. The total yield of ethylene and acetylene is 15.6%. The reduced flow rate of feed improves the conversion of ethane, carbon dioxide and the yield of acetylene, and induces carbon deposit as well

Evolution of the Ethane Architecture

National Research Council Canada - National Science Library

Casado, Martin; Shenker, Scott

2009-01-01

The Ethane architecture, developed at Stanford University, demonstrated that a novel approach to building secure networks could support superior low-level security and flexible policy-based control over individual flows...

Biogeochemistry of Halogenated Hydrocarbons

Science.gov (United States)

Adriaens, P.; Gruden, C.; McCormick, M. L.

2003-12-01

Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

Independent Evolution of Six Families of Halogenating Enzymes.

Science.gov (United States)

Xu, Gangming; Wang, Bin-Gui

2016-01-01

Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

Reconsideration of methane isotope signature as a criterion for the genesis of natural gas: influence of migration on isotopic signatures

International Nuclear Information System (INIS)

Pernaton, E.; Prinzhofer, A.; Schneider, F.

1996-01-01

Experiments were performed in the purpose of studying the isotopic consequences of the diffusional transport of hydrocarbon gases through sediment rocks. Linked to a numerical model, these gas diffusion experiments through as shale porous plug allowed us to correlate porosity and diffusivity of the migration medium. Significant isotopic fractionations (carbon and hydrogen) of methane, and ethane at a lesser degree were observed. This is in contradiction with the actual dogma of isotope geochemistry of natural gases which claims that no fractionation occurs during gas migration. The genetic characterization of natural gases by using the isotopic signature of methane appears as an ambiguous method. (author)

Exhaled ethane: an in vivo biomarker of lipid peroxidation in interstitial lung diseases.

Science.gov (United States)

Kanoh, Soichiro; Kobayashi, Hideo; Motoyoshi, Kazuo

2005-10-01

Oxidative stress plays a role in the pathogenesis and progression of interstitial lung disease (ILD). Exhaled ethane is a product of lipid peroxidation that has been proposed as a biomarker of oxidative stress in vivo. To determine whether the exhaled ethane level is elevated in patients with ILD and to compare it with other clinical parameters. Breath samples were collected from 34 patients with ILD, including 13 with idiopathic pulmonary fibrosis (IPF), 9 patients with cryptogenic organizing pneumonia, 6 patients with collagen vascular disease-associated interstitial pneumonia, and 6 patients with pulmonary sarcoidosis. Gas samples were obtained at hospital admission and after 3 weeks. After each expired sample was concentrated using a trap-and-purge procedure, the ethane level was analyzed by gas chromatography. Exhaled ethane levels were elevated in ILD patients (n = 34, mean +/- SD, 8.5 +/- 8.0 pmol/dL) compared with healthy volunteers (n = 16, 2.9 +/- 1.0 pmol/dL; p ethane levels were largely consistent with the clinical course. Four patients with IPF who had persistently high ethane levels died or deteriorated, whereas those with ethane levels ethane concentrations were positively correlated with levels of lactate dehydrogenase (Spearman rank correlation coefficient [rs], 0.28, p = 0.026) and C-reactive protein (rs, 0.38, p = 0.025) and were inversely correlated with Pa(O2) (rs, - 0.40, p = 0.0026). Patients showing increased uptake on (67)Ga scintigraphy demonstrated higher ethane levels (n = 19, 7.5 +/- 5.7 pmol/dL) compared with those who did not show increased uptake on scintigraphy (n = 10, 3.0 +/- 2.4 pmol/dL; p ethane is elevated in patients with ILD and is correlated with the clinical outcome, suggesting that it provides useful information about ongoing oxidative stress, and thereby disease activity and severity in ILD.

Methyl-coenzyme M reductase from methanogenic archaea: isotope effects on label exchange and ethane formation with the homologous substrate ethyl-coenzyme M.

Science.gov (United States)

Scheller, Silvan; Goenrich, Meike; Thauer, Rudolf K; Jaun, Bernhard

2013-10-09

Ethyl-coenzyme M (CH3CH2-S-CH2CH2-SO3(-), Et-S-CoM) serves as a homologous substrate for the enzyme methyl-coenzyme M reductase (MCR) resulting in the product ethane instead of methane. The catalytic reaction proceeds via an intermediate that already contains all six C-H bonds of the product. Because product release occurs after a second, rate-limiting step, many cycles of intermediate formation and reconversion to substrate occur before a substantial amount of ethane is released. In deuterated buffer, the intermediate becomes labeled, and C-H activation in the back reaction rapidly leads to labeled Et-S-CoM, which enables intermediate formation to be detected. Here, we present a comprehensive analysis of this pre-equilibrium. (2)H- and (13)C-labeled isotopologues of Et-S-CoM were used as the substrates, and the time course of each isotopologue was followed by NMR spectroscopy. A kinetic simulation including kinetic isotope effects allowed determination of the primary and α- and β-secondary isotope effects for intermediate formation and for the C-H/C-D bond activation in the ethane-containing intermediate. The values obtained are in accordance with those found for the native substrate Me-S-CoM (see preceding publication, Scheller, S.; Goenrich, M.; Thauer, R. K.; Jaun, B. J. Am. Chem. Soc. 2013, 135, DOI: 10.1021/ja406485z) and thus imply the same catalytic mechanism for both substrates. The experiment by Floss and co-workers, demonstrating a net inversion of configuration to chiral ethane with CH3CDT-S-CoM as the substrate, is compatible with the observed rapid isotope exchange if the isotope effects measured here are taken into account.

Adsorptive separation of ethylene/ethane mixtures using carbon nanotubes: a molecular dynamics study

International Nuclear Information System (INIS)

Tian, Xingling; Zhou, Bo; Wang, Zhigang; Yang, Zaixing; Xiu, Peng

2013-01-01

Ethylene/ethane separation is a very important process in the chemical industry. Traditionally, this process is achieved by cryodistillation, which is extremely energy-intensive. The adsorptive separation is an energy-saving and environmentally benign alternative. In this study, we employ molecular dynamics simulations to study the competitive adsorption of an equimolar mixture of gaseous ethane and ethylene inside single-walled carbon nanotubes (SWNTs) of different diameters at room temperature. We find that for narrow SWNTs, i.e. the (6, 6) and (7, 7) SWNTs, the selectivities towards ethane, f selec , can reach values of 3.1 and 3.7, respectively. Such high selectivities are contrary to the opinion of many researchers that the adsorptive separation of an ethylene/ethane mixture by means of dispersion interaction is difficult due to the same carbon number of ethane and ethylene. The key for our observation is that the role of dispersion interaction of ethane's additional two hydrogen atoms with the SWNT becomes significant under extreme confinement. Interestingly, the (8, 8) SWNT prefers ethylene to ethane with f selec = 0.6. For wider SWNTs, f selec converges to ∼1. The mechanisms behind these observations, as well as the kinetics of single-file nanopore filling and kinetics of confined gas molecules are discussed. Our findings suggest that efficient ethane/ethylene separation can be achieved by using bundles/membranes of SWNTs with appropriate diameters. (paper)

Passivation of quartz for halogen-containing light sources

Science.gov (United States)

Falkenstein, Zoran

1999-01-01

Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

Characteristics of atmospheric non-methane hydrocarbons in Foshan City, China.

Science.gov (United States)

Tan, Jihua; Guo, Songjun; Ma, Yongliang; He, Kebin; Yang, Fumo; Yu, Yongchang; Wang, Jiewen

2011-12-01

Foshan is the most air-polluted city in Pearl River Delta. Non-methane hydrocarbons (NMHCs) were investigated for the first time in Foshan in winter 2008. Ethene, ethane, ethyne, propane, i-pentane, and toluene were the most abundant hydrocarbons and observed to be higher in Foshan than those in many other cities in China. Different from other cities, ethene and ethane were observed to be the two highest compounds in Foshan. Generally, the most abundant hydrocarbons showed high mixing ratios in the morning (0930-1030 hours), decreased to the lowest level in the afternoon (1430-1530 hours), and increased to higher value in the evening (1930-2030 hours). But i-pentane exhibited a different diurnal pattern with the highest level (13.4 ± 5.8 ppbv) in the afternoon, implying the acceleration of solvent evaporation resulting from higher temperature. Correlation coefficients (R(2) = 66% for n = 6 at 95% confidence level) of the individual hydrocarbons with ethyne and i-pentane indicated vehicular emissions were the main sources of ethene, propene, i-butene, isoprene, benzene and toluene, while gasoline evaporation was responsible for n-pentane, n-hexane, and n-heptane. The good correlation of most of the hydrocarbons with ethyne, indicating vehicular emissions, were the main sources of NMHCs. B/T ratio was 0.36 ± 0.06, implying vehicular emissions acted as the major contributors as well as additional emissions of toluene emitted from solvent usage. According to investigation, it also suggested that LPG leakage was the main source of propane, while NG leakage was responsible for ethane in Foshan City.

Organic halogens in spruce forest throughfall

DEFF Research Database (Denmark)

Öberg, G.; Johansen, C.; Grøn, C.

1998-01-01

. No relationship between the position of the collectors and the forest edge or dominating wind-direction was found, suggesting that dry deposition was not a major source. The concentration of organic halogens was related to that of organic carbon and decreased from the tree-trunk and outwards. In addition......, the concentrations were higher during the growing season than during the dormant season. This indicates that the major part of the organic carbon and organic halogens in spruce forest throughfall originates from canopy leachates or other internal sources. (C) 1998 Elsevier Science Ltd.......Deposition of dissolved organic halogens by throughfall was determined in a small spruce forest site in Denmark (56 degrees 28'N, 8 degrees 24'E). The mean annual deposition of dissolved organic halogens was 377 g ha(-1)yr(-1), and larger than the general deposition by precipitation...

Formation of a new benzene-ethane co-crystalline structure under cryogenic conditions.

Science.gov (United States)

Vu, Tuan Hoang; Cable, Morgan L; Choukroun, Mathieu; Hodyss, Robert; Beauchamp, Patricia

2014-06-12

We report the first experimental finding of a solid molecular complex between benzene and ethane, two small apolar hydrocarbons, at atmospheric pressure and cryogenic temperatures. Considerable amounts of ethane are found to be incorporated inside the benzene lattice upon the addition of liquid ethane onto solid benzene at 90-150 K, resulting in formation of a distinctive co-crystalline structure that can be detected via micro-Raman spectroscopy. Two new features characteristic of these co-crystals are observed in the Raman spectra at 2873 and 1455 cm(-1), which are red-shifted by 12 cm(-1) from the υ1 (a1g) and υ11 (eg) stretching modes of liquid ethane, respectively. Analysis of benzene and ethane vibrational bands combined with quantum mechanical modeling of isolated molecular dimers reveal an interaction between the aromatic ring of benzene and the hydrogen atoms of ethane in a C-H···π fashion. The most favored configuration for the benzene-ethane dimer is the monodentate-contact structure, with a calculated interaction energy of 9.33 kJ/mol and an equilibrium bonding distance of 2.66 Å. These parameters are comparable to those for a T-shaped co-crystalline complex between benzene and acetylene that has been previously reported in the literature. These results are relevant for understanding the hydrocarbon cycle of Titan, where benzene and similar organics may act as potential hydrocarbon reservoirs due to this incorporation mechanism.

Characterization of methane emissions from five cold heavy oil production with sands (CHOPS) facilities.

Science.gov (United States)

Roscioli, Joseph R; Herndon, Scott C; Yacovitch, Tara I; Knighton, W Berk; Zavala-Araiza, Daniel; Johnson, Matthew R; Tyner, David R

2018-03-07

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical "fingerprint" associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions. Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government's goal of reducing methane emissions by 40-45% below 2012 levels within 8 yr.

New Type of Halogen Bond: Multivalent Halogen Interacting with π- and σ-Electrons

Directory of Open Access Journals (Sweden)

Sławomir J. Grabowski

2017-12-01

Full Text Available MP2/aug-cc-pVTZ calculations were performed for complexes of BrF3 and BrF5 acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its σ-bond, while in remaining moieties—in complexes of hydrocarbons; such an electron transfer follows from π-electrons. The complexes are linked by a kind of the halogen bond that is analyzed for the first time in this study, i.e., it is the link between the multivalent halogen and π or σ-electrons. The nature of such a halogen bond is discussed, as well as various dependencies and correlations are presented. Different approaches are applied here, the Quantum Theory of Atoms in Molecules, Natural Bond Orbital method, the decomposition of the energy of interaction, the analysis of electrostatic potentials, etc.

Experimental and computational evidence of halogen bonds involving astatine

Science.gov (United States)

Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

2018-03-01

The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

Science.gov (United States)

Oliveira, Vytor; Cremer, Dieter

2017-08-01

Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

Laboratory Studies of Ethane Ice Relevant to Outer Solar System Surfaces

Science.gov (United States)

Moore, Marla H.; Hudson, Reggie; Raines, Lily

2009-01-01

Oort Cloud comets, as well as TNOs Makemake (2045 FYg), Quaoar, and Pluto, are known to contain ethane. However, even though this molecule is found on several outer Solar System objects relatively little information is available about its amorphous and crystalline phases. In new experiments, we have prepared ethane ices at temperatures applicable to the outer Solar System, and have heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry using mid-IR spectroscopy (2.2 - 16.6 microns). Included in our work is the meta-stable phase that exists at 35 - 55 K. These results, including newly obtained optical constants, are relevant to ground-based observational campaigns, the New Horizons mission, and supporting laboratory work. An improved understanding of solid-phase ethane may contribute to future searches for this and other hydrocarbons in the outer Solar System.

Theoretical analysis of the rotational barrier of ethane.

Science.gov (United States)

Mo, Yirong; Gao, Jiali

2007-02-01

The understanding of the ethane rotation barrier is fundamental for structural theory and the conformational analysis of organic molecules and requires a consistent theoretical model to differentiate the steric and hyperconjugation effects. Due to recently renewed controversies over the barrier's origin, we developed a computational approach to probe the rotation barriers of ethane and its congeners in terms of steric repulsion, hyperconjugative interaction, and electronic and geometric relaxations. Our study reinstated that the conventional steric repulsion overwhelmingly dominates the barriers.

Increased ethane exhalation, an in vivo index of lipid peroxidation, in alcohol-abusers.

Science.gov (United States)

Lettéron, P; Duchatelle, V; Berson, A; Fromenty, B; Fisch, C; Degott, C; Benhamou, J P; Pessayre, D

1993-01-01

Ethane exhalation was measured in 42 control subjects, 52 patients with various non-alcoholic liver diseases, and 89 alcohol abusers who had been admitted to hospital for alcohol withdrawal and assessment of liver disease (six with normal liver tests, 10 with steatosis with or without fibrosis, six with alcoholic hepatitis, 29 with cirrhosis, 34 with both cirrhosis and alcoholic hepatitis, and four with both cirrhosis and a hepatocellular carcinoma). Ethane exhalation was similar in control subjects and in patients with non-alcoholic liver diseases, but was five times higher in alcohol abusers. Ethane exhalation in alcohol abusers was significantly, but very weakly, correlated with the daily ethanol intake before hospital admission, and the histological score for steatosis, but not with the inflammation or alcoholic hepatitis scores. Ethane exhalation was inversely correlated with the duration of abstinence before the test. In nine alcoholic patients, the exhalation of ethane was measured repeatedly, and showed slow improvement during abstinence. Ethane exhalation was significantly but weakly correlated with the Pugh's score in patients with alcoholic cirrhosis. It is concluded that the mean ethane exhalation is increased in alcohol abusers. One of the possible mechanisms may be the presence of oxidizable fat in the liver. The weak correlation with the Pugh's score is consistent with the contribution of many other factors in the progression to severe liver disease. PMID:8472992

Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

Science.gov (United States)

Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

2017-03-21

During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

The halogen bond: Nature and applications

Science.gov (United States)

Costa, Paulo J.

2017-10-01

The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

Science.gov (United States)

Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

2017-04-26

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

Molecular activation analysis for organo-halogen contaminants in yogurt

International Nuclear Information System (INIS)

Zhang Hong; Chai Zhifang

2004-01-01

The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

Energy Technology Data Exchange (ETDEWEB)

John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

2002-06-01

Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

Ethane Ices in the Outer Solar System: Spectroscopy and Chemistry

Science.gov (United States)

Hudson, R. L.; Moore, M. H.; Raines, L. L.

2009-01-01

We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons

Kinetic modeling of ethane pyrolysis at high conversion.

Science.gov (United States)

Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang; Carstensen, Hans-Heinrich; Dean, Anthony M

2011-09-29

The primary objective of this study is to develop an improved first-principle-based mechanism that describes the molecular weight growth kinetics observed during ethane pyrolysis. A proper characterization of the kinetics of ethane pyrolysis is a prerequisite for any analysis of hydrocarbon pyrolysis and oxidation. Flow reactor experiments were performed with ~50/50 ethane/nitrogen mixtures with temperatures ranging from 550 to 850 °C at an absolute pressure of ~0.8 atm and a residence time of ~5 s. These conditions result in ethane conversions ranging from virtually no reaction to ~90%. Comparisons of predictions using our original mechanism to these data yielded very satisfactory results in terms of the temperature dependence of ethane conversion and prediction of the major products ethylene and hydrogen. However, there were discrepancies in some of the minor species concentrations that are involved in the molecular weight growth kinetics. We performed a series of CBS-QB3 analyses for the C(3)H(7), C(4)H(7), and C(4)H(9) potential energy surfaces to better characterize the radical addition reactions that lead to molecular weight growth. We also extended a published C(6)H(9) PES to include addition of vinyl to butadiene. The results were then used to calculate pressure-dependent rate constants for the multiple reaction pathways of these addition reactions. Inclusion of the unadjusted rate constants resulting from these analyses in the mechanism significantly improved the description of several of the species involved in molecular weight growth kinetics. We compare the predictions of this improved model to those obtained with a consensus model recently published as well as to ethane steam cracking data. We find that a particularly important reaction is that of vinyl addition to butadiene. Another important observation is that several radical addition reactions are partially equilibrated. Not only does this mean that reliable thermodynamic parameters are essential

Halogens in chondritic meteorites and terrestrial accretion

Science.gov (United States)

Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

2017-11-01

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

Organic halogen compounds in the environment

International Nuclear Information System (INIS)

1979-07-01

There are 20 research reports on selected problems concerning the analysis, the occurence, and the behaviour of a wide spectrum of organic halogen compounds. The work was carried out in the framework of the project 'Organic Halogen Compounds in the Environment', financed by the BMFT, between 1975 and 1978. (orig.) [de

Process for removal of hydrogen halides or halogens from incinerator gas

Science.gov (United States)

Huang, H.S.; Sather, N.F.

1987-08-21

A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Portable optical spectroscopy for accurate analysis of ethane in exhaled breath

Science.gov (United States)

Patterson, Claire S.; McMillan, Lesley C.; Longbottom, Christopher; Gibson, Graham M.; Padgett, Miles J.; Skeldon, Kenneth D.

2007-05-01

We report on a maintenance-free, ward-portable, tunable diode laser spectroscopy system for the ultra-sensitive detection of ethane gas. Ethane is produced when cellular lipids are oxidized by free radicals. As a breath biomarker, ethane offers a unique measure of such oxidative stress. The ability to measure real-time breath ethane fluctuations will open up new areas in non-invasive healthcare. Instrumentation for such a purpose must be highly sensitive and specific to the target gas. Our technology has a sensitivity of 70 parts per trillion and a 1 s sampling rate. Based on a cryogenically cooled lead-salt laser, the instrument has a thermally managed closed-loop refrigeration system, eliminating the need for liquid coolants. Custom LabVIEW software allows automatic control by a laptop PC. We have field tested the instrument to ensure that target performance is sustained in a range of environments. We outline the novel applications underway with the instrument based on an in vivo clinical assessment of oxidative stress.

Experimental study of adiabatic cellular premixed flames of methane (ethane, propane) + oxygen + carbon dioxide mixtures

NARCIS (Netherlands)

Konnov, A.A.; Dyakov, I.V.

2007-01-01

Experimental studies of adiabatic cellular flames of CH4 + O2 + CO2, C2H6 + O2 + CO2, and C3H8 + O2 + CO2 are presented. Visual and photographic observations of the flames were performed to quantify their cellular structure. Non-stretched flames of methane and propane were stabilized at atmospheric

Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

Science.gov (United States)

Ford, Melissa Coates; Ho, P Shing

2016-03-10

The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

Manufacture of Methane Hydrate using Carbon Nano Tubes

International Nuclear Information System (INIS)

Park, Sung Seek

2010-02-01

Methane hydrate is formed by physical binding between water molecule and gas such as methane, ethane, propane, or carbon dioxide, etc., which is captured in the cavities of water molecule under the specific temperature and pressure. More than 99% of naturally produced methane hydrate consists of methane, and is widely dispersed in the continental slope and continental Shelf of the Pacific and the Atlantic, the Antarctica etc. The reserve of fossil fuel is 500 billion carbon ton and the reserve of methane is 360 million carbon ton. The reserve of gas hydrate is more than 1 trillion carbon ton, which is twice the fossil fuel. Therefore, natural gas hydrate as a kind of gas hydrate is expected to replace fossil fuel as new energy source of 21st century. Also 1 m 3 hydrate of pure methane can be decomposed to the maximum of 216 m 3 methane at standard condition. If these characteristics of hydrate are reversely utilized, natural gas is fixed into water in the form of hydrate solid. Therefore, the hydrate is considered to be a great way to transport and store natural gas in large quantity. Especially the transportation cost is known to be 18∼25% less than the liquefied transportation. However, when natural gas hydrate is artificially formed, its reaction time may be too long and the gas consumption in water becomes relatively low, because the reaction rate between water and gas is low. Therefore, for the practical purpose in the application, the present investigation focuses on the rapid production of hydrates and increases gas consumption by adding MWCNT and NaCl into pure water. The results show that the equilibrium pressure in seawater is more higher than that in pure water, and methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 9K or above in seawater and 8K or above in pure water, respectively. Also, amount of consumed gas volume in pure water is more higher that in seawater at the same experimental conditions

Complete biological reductive transformation of tetrachloroethene to ethane.

Science.gov (United States)

de Bruin, W P; Kotterman, M J; Posthumus, M A; Schraa, G; Zehnder, A J

1992-01-01

Reductive dechlorination of tetrachloroethene (perchloroethylene; PCE) was observed at 20 degrees C in a fixed-bed column, filled with a mixture (3:1) of anaerobic sediment from the Rhine river and anaerobic granular sludge. In the presence of lactate (1 mM) as an electron donor, 9 microM PCE was dechlorinated to ethene. Ethene was further reduced to ethane. Mass balances demonstrated an almost complete conversion (95 to 98%), with no chlorinated compounds remaining (less than 0.5 micrograms/liter). When the temperature was lowered to 10 degrees C, an adaptation of 2 weeks was necessary to obtain the same performance as at 20 degrees C. Dechlorination by column material to ethene, followed by a slow ethane production, could also be achieved in batch cultures. Ethane was not formed in the presence of bromoethanesulfonic acid, an inhibitor of methanogenesis. The high dechlorination rate (3.7 mumol.l-1.h-1), even at low temperatures and considerable PCE concentrations, together with the absence of chlorinated end products, makes reductive dechlorination an attractive method for removal of PCE in bioremediation processes. PMID:1622277

Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

Directory of Open Access Journals (Sweden)

Tjarda J. Roberts

2018-02-01

Full Text Available Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA, a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2. Measurements in grounding plume (at 5 ppmv SO2 about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere.

78 FR 62323 - MarkWest Liberty Ethane Pipeline L.L.C.; Notice of Petition for Declaratory Order

Science.gov (United States)

2013-10-16

... Ethane Pipeline L.L.C.; Notice of Petition for Declaratory Order Take notice that on October 3, 2013...), MarkWest Liberty Ethane Pipeline L.L.C. (MarkWest) filed a petition requesting a declaratory order approving the overall tariff and rate structure for a new ethane pipeline system that will transport ethane...

Remote Sensing and Sea-Truth Measurements of Methane Flux to the Atmosphere (HYFLUX project)

Energy Technology Data Exchange (ETDEWEB)

Ian MacDonald

2011-05-31

A multi-disciplinary investigation of distribution and magnitude of methane fluxes from seafloor gas hydrate deposits in the Gulf of Mexico was conducted based on results obtained from satellite synthetic aperture radar (SAR) remote sensing and from sampling conducted during a research expedition to three sites where gas hydrate occurs (MC118, GC600, and GC185). Samples of sediments, water, and air were collected from the ship and from an ROV submersible using sediments cores, niskin bottles attached to the ROV and to a rosette, and an automated sea-air interface collector. The SAR images were used to quantify the magnitude and distribution of natural oil and gas seeps that produced perennial oil slicks on the ocean surface. A total of 176 SAR images were processed using a texture classifying neural network algorithm, which segmented the ocean surface into oil-free and oil-covered water. Geostatistical analysis indicates that there are a total of 1081 seep formations distributed over the entire Gulf of Mexico basin. Oil-covered water comprised an average of 780.0 sq. km (sd 86.03) distributed with an area of 147,370 sq. km. Persistent oil and gas seeps were also detected with SAR sampling on other ocean margins located in the Black Sea, western coast of Africa, and offshore Pakistan. Analysis of sediment cores from all three sites show profiles of sulfate, sulfide, calcium and alkalinity that indicated anaerobic oxidation of methane with precipitation of authigenic carbonates. Difference among the three sampling sites may reflect the relative magnitude of methane flux. Methane concentrations in water column samples collected by ROV and rosette deployments from MC118 ranged from {approx}33,000 nM at the seafloor to {approx}12 nM in the mixed layer with isolated peaks up to {approx}13,670 nM coincident with the top of the gas hydrate stability field. Average plume methane, ethane, and propane concentrations in the mixed layer are 7, 630, and 9,540 times saturation

Metagenomic analysis of the rumen microbial community following inhibition of methane formation by a halogenated methane analogue

Directory of Open Access Journals (Sweden)

Stuart E Denman

2015-10-01

Full Text Available Japanese goats fed a diet of 50% Timothy grass and 50% concentrate with increasing levels of the anti-methanogenic compound, bromochloromethane (BCM were investigated with respect to the microbial shifts in the rumen. Microbial ecology methods identified many species that exhibited positive and negative responses to the increasing levels of BCM. The methane-inhibited rumen appeared to adapt to the higher H2 levels by shifting fermentation to propionate which was mediated by an increase in the population of hydrogen-consuming Prevotella and Selenomonas spp. Metagenomic analysis of propionate production pathways was dominated by genomic content from these species. Reductive acetogenic marker gene libraries and metagenomics analysis indicate that reductive acetogenic species do not play a major role in the BCM treated rumen.

Atmospheric methane isotopic record favors fossil sources flat in 1980s and 1990s with recent increase

Science.gov (United States)

Rice, Andrew L.; Butenhoff, Christopher L.; Teama, Doaa G.; Röger, Florian H.; Khalil, M. Aslam K.; Rasmussen, Reinhold A.

2016-09-01

Observations of atmospheric methane (CH4) since the late 1970s and measurements of CH4 trapped in ice and snow reveal a meteoric rise in concentration during much of the twentieth century. Since 1750, levels of atmospheric CH4 have more than doubled to current globally averaged concentration near 1,800 ppb. During the late 1980s and 1990s, the CH4 growth rate slowed substantially and was near or at zero between 1999 and 2006. There is no scientific consensus on the drivers of this slowdown. Here, we report measurements of the stable isotopic composition of atmospheric CH4 (13C/12C and D/H) from a rare air archive dating from 1977 to 1998. Together with more modern records of isotopic atmospheric CH4, we performed a time-dependent retrieval of methane fluxes spanning 25 y (1984-2009) using a 3D chemical transport model. This inversion results in a 24 [18, 27] Tg y-1 CH4 increase in fugitive fossil fuel emissions since 1984 with most of this growth occurring after year 2000. This result is consistent with some bottom-up emissions inventories but not with recent estimates based on atmospheric ethane. In fact, when forced with decreasing emissions from fossil fuel sources our inversion estimates unreasonably high emissions in other sources. Further, the inversion estimates a decrease in biomass-burning emissions that could explain falling ethane abundance. A range of sensitivity tests suggests that these results are robust.

Growth potential in gas plant ethane production and the impact on propane import trends

International Nuclear Information System (INIS)

Lippe, D.L.

1996-01-01

In varying degrees in most ethylene plants, ethane and propane are used interchangeably as feedstocks. During the next five years, several new ethylene plants will be built in the Gulf Coast area. Most of these plants will be based on LPG feedstocks and will have some flexibility to operate with ethane and propane feedstocks. The completion of new ethylene plants will increase feedstock demand for ethane by 65--90 Mbpd by 1998 and by an additional 50--80 Mbpd by 2000. Thus, the availability of ethane will have a significant impact on Gulf Coast waterborne propane import requirements. Sustained growth in the gas processing industry's ethane recovery capability will effectively minimize waterborne propane import requirements for the next five to ten years. Petral Worldwide's approach to feedstock supply analysis highlights investment opportunities in domestic supply sources. Projects of these types will also limit a growth dependence on NGL feedstock supplies from politically unstable supply sources in North Africa and the Middle East. This paper examines the potential for growth in the gas processing industry's ethane recovery capability and the impact on Gulf Coast feedstock markets

Stability conditions and guest distribution of the methane + ethane + propane hydrates or semiclathrates in the presence of tetrahydrofuran or quaternary ammonium salts

International Nuclear Information System (INIS)

Lee, Seungmin; Lee, Youngjun; Park, Sungwon; Kim, Yunju; Cha, Inuk; Seo, Yongwon

2013-01-01

Highlights: • We examined the stability conditions and guest distributions of natural gas hydrates. • THF, TBAB, and TBAF could remarkably stabilize the hydrate dissociation conditions. • Preferential occupation of CH 4 molecules was observed at the stoichiometric concentrations. -- Abstract: In this study, the stability conditions and guest distributions of methane (CH 4 ) + ethane (C 2 H 6 ) + propane (C 3 H 8 ) hydrates or semiclathrates are examined in the presence of tetrahydrofuran (THF) and quaternary ammonium salts such as tetra-n-butylammonium bromide (TBAB) and tetra-n-butylammonium fluoride (TBAF) through thermodynamic and spectroscopic analyses. The three-phase equilibria of hydrate or semiclathrate (H), liquid water (L W ), and vapor (V) for the quinary CH 4 + C 2 H 6 + C 3 H 8 + THF + water, CH 4 + C 2 H 6 + C 3 H 8 + TBAB + water, and CH 4 + C 2 H 6 + C 3 H 8 + TBAF + water mixtures with various concentrations were experimentally measured in order to determine the hydrate or semiclathrate stability conditions. The experimental results demonstrated that all thermodynamic promoters such as THF, TBAB, and TBAF used in this study could remarkably stabilize the hydrate dissociation conditions even though the degree of stabilization was dependent on the type of promoters and on the concentrations of each promoter used. From the 13 C NMR analysis, preferential occupation of CH 4 molecules in the hydrate or semiclathrate lattices was observed at the stoichiometric concentrations of each hydrate or semiclathrate structure. However, at the THF mole fraction lower than 0.056, the large cages of structure II were shared by CH 4 , C 2 H 6 , C 3 H 8 , and THF molecules, whereas the small cages were occupied by only CH 4 molecules. The results given in this study are very useful in understanding the thermodynamic stability, structural characteristics, and guest distribution of the hydrates or semiclathrates with multi-components in the presence of

Retention of Halogens in Waste Glass

Energy Technology Data Exchange (ETDEWEB)

Hrma, Pavel R.

2010-05-01

In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

Re/HZSM-5: a new catalyst for ethane aromatization with improved stability

DEFF Research Database (Denmark)

Krogh, Anne; Hansen, Thomas W.; Christensen, Claus Hviid

2003-01-01

Rhenium-impregnated HZSM-5 is found to be a promising catalyst for ethane aromatization. The Re–HZSM-5 catalyst deactivates significantly slower than well-known ethane aromatization Zn–HZSM-5 catalyst. Product selectivities for the two catalysts are similar, indicating that the shape selectivity...

Halogen-Mediated Conversion of Hydrocarbons to Commodities.

Science.gov (United States)

Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

2017-03-08

Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC.

Science.gov (United States)

Huang, Lili; Lu, Juan; Di, Bin; Feng, Fang; Su, Mengxiang; Yan, Fang

2011-09-01

Monodisperse spherical periodic mesoporous organosilicas (PMOs) with ethane integrated in the framework were synthesized and their application as stationary phase for chromatographic separation is demonstrated. The ethane-PMOs were prepared by condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) in basic condition using octadecyltrimethylammonium chloride (C(18)TMACl) as template and ethanol as co-solvent. The morphology and mesoporous structure of ethane-PMOs were controlled under different concentrations of sodium hydroxide (NaOH) and EtOH. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis showed that ethane-PMOs have spherical morphology, uniform particle distribution, highly ordered pore structure, high surface area and narrow pore-size distribution. The column packed with these materials exhibits good permeability, high chemical stability and good selectivity of mixtures of aromatic hydrocarbons in normal phase high-performance liquid chromatography (HPLC). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methane Occurrence in a Drinking Water Aquifer Before and During Natural Gas Production from the Marcellus Shale

Science.gov (United States)

Saiers, J. E.; Barth-Naftilan, E.

2017-12-01

More than 4,000 thousand wells have punctured aquifers of Pennsylvania's northern tier to siphon natural gas from the underlying Marcellus Shale. As drilling and hydraulic fracturing ramped up a decade ago, homeowner reports of well water contamination by methane and other contaminants began to emerge. Although made infrequently compared to the number of gas wells drilled, these reports were troubling and motivated our two-year, prospective study of groundwater quality within the Marcellus Shale Play. We installed multi-level sampling wells within a bedrock aquifer of a 25 km2 area that was targeted for shale gas development. These wells were sampled on a monthly basis before, during, and after seven shale gas wells were drilled, hydraulically fractured, and placed into production. The groundwater samples, together with surface water samples collected from nearby streams, were analyzed for hydrocarbons, trace metals, major ions, and the isotopic compositions of methane, ethane, water, strontium, and dissolved inorganic carbon. With regard to methane in particular, concentrations ranged from under 0.1 to over 60 mg/L, generally increased with aquifer depth, and, at some sites, exhibited considerable temporal variability. The isotopic composition of methane and hydrocarbon ratios also spanned a large range, suggesting that methane origins are diverse and, notably, shift on the time scale of this study. We will present inferences on factors governing methane occurrence across our study area by interpreting time-series data on methane concentrations and isotopic composition in context of local hydrologic variation, companion measurements of groundwater chemistry, and the known timing of key stages of natural gas extraction.

E. S. R. studies of halogenated pyrimidines in. gamma. -irradiated alkaline glasses. [Halogenated uracil bases; bromouridine; bromodeoxyuridine

Energy Technology Data Exchange (ETDEWEB)

Simpson, L D; Zimbrick, J D [Kansas Univ., Lawrence (USA)

1975-11-01

The reactions of mobile electrons (e/sup -//sub m/) and oxygen radical anions (O./sup -/) with halogenated bases and nucleosides have been studied in ..gamma..-irradiated alkaline glasses by e.s.r. and specific halogen-ion electrode techniques. It was shown that electrons react with halogenated uracil bases (XUr where X = Cl, Br, I but not F) by dissociative electron attachment to form uracil-5-yl radicals (U.) and halogen anions. The relative rates of reaction of e/sup -//sub m/ with XUr decreased in the sequence BrUr > ClUr > FUr > IUr. Thermal annealing studies carried out on U. in H/sub 2/O and D/sub 2/O matrices supported the hypothesis that U. in H/sub 2/O hydrates across the 5-6 double bond in the temperature region 135/sup 0/ to 155/sup 0/ K, and deuterates to a much smaller extent in D/sub 2/O at temperatures above 155/sup 0/ K. Studies on bromouridine and bromodeoxyuridine suggested that e/sup -/sub(m) reacts with the base moieties to form U. type radicals which abstract H. from the sugar moieties of adjacent nucleosides.

Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect

DEFF Research Database (Denmark)

Gorham, Katrine A; Andersen, Mads Peter Sulbæk; Meinardi, Simone

2009-01-01

The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were...... found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled...... hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO(2) and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these findings, ethane and n-pentane do not appear to be markers of airway...

Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect.

Science.gov (United States)

Gorham, Katrine A; Sulbaek Andersen, Mads P; Meinardi, Simone; Delfino, Ralph J; Staimer, Norbert; Tjoa, Thomas; Rowland, F Sherwood; Blake, Donald R

2009-02-01

The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO(2) and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these findings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress.

Fugitive Emissions from the Bakken Shale Illustrate Role of Shale Production in Global Ethane Shift

Science.gov (United States)

Kort, E. A.; Smith, M. L.; Murray, L. T.; Gvakharia, A.; Brandt, A. R.; Peischl, J.; Ryerson, T. B.; Sweeney, C.; Travis, K.

2016-01-01

Ethane is the second most abundant atmospheric hydrocarbon, exerts a strong influence on tropospheric ozone, and reduces the atmosphere's oxidative capacity. Global observations showed declining ethane abundances from 1984 to 2010, while a regional measurement indicated increasing levels since 2009, with the reason for this subject to speculation. The Bakken shale is an oil and gas-producing formation centered in North Dakota that experienced a rapid increase in production beginning in 2010. We use airborne data collected over the North Dakota portion of the Bakken shale in 2014 to calculate ethane emissions of 0.23 +/- 0.07 (2 sigma) Tg/yr, equivalent to 1-3% of total global sources. Emissions of this magnitude impact air quality via concurrent increases in tropospheric ozone. This recently developed large ethane source from one location illustrates the key role of shale oil and gas production in rising global ethane levels.

Supercritical extraction of lycopene from tomato industrial wastes with ethane.

Science.gov (United States)

Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

2012-07-11

Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

Hydrogen--deuterium exchange in saturated hydrocarbons on α-chromia catalyst

International Nuclear Information System (INIS)

Kalman, J.; Guczi, L.

1977-01-01

The kinetics of hydrogen--deuterium exchange in methane, ethane, and propane have been studied with unsupported α-chromia as catalyst in the temperature range of 598 to 688 0 K. The apparent activation energies for methane, ethane, and propane are 88, 130, and 84 kJ mol -1 , respectively, similar to those found on chromia gel. The order of reaction with respect to hydrocarbons and deuterium has been determined as also having the kinetic isotope effect. The main initial products are CH 3 D and CD 4 with methane, C 2 H 4 D 2 and C 2 D 6 with ethane, and C 3 H 7 D and C 3 D 8 with propane. A change in product distribution as a function of temperature, conversion, aging, and oxygen--deuterium treatment has been observed. In agreement with the kinetic data and the effect of oxygen, Cr 3+ has been assumed as the active species of the chromia catalyst, whereas Cr 2+ is an inactive site on the surface. There is no direct proof that chromium ion in a valence state higher than 3+ plays an important role in the exchange reaction. It was established that dual Cr 3+ -- Cr 3+ sites are responsible for the formation of ethane-d 2 . After a long deuterium treatment the number of dual sites is decreased, the effect being revealed in the decreased rate of exchange and the small amount of ethane-d 2 . On the contrary, the formation of methane-d 4 is interpreted by the formation of Cr = C bonds by analogy with homogeneous complexes. In the case of propane, the exchange reaction can be adequately interpreted by a π-allyl mechanism

Na-montmorillonite hydrates under ethane rich reservoirs: NPzzT and MuPzzT simulations

OpenAIRE

Odriozola, G.; Aguilar, J. F.; López-Lemus, J.

2005-01-01

Na-montmorillonite hydrates in presence of ethane molecules are studied by means of hybrid Monte Carlo simulations in the NPzzT and MuPzzT ensembles. The NPzzT ensemble allows us to study the interlaminar distance as a function of water and ethane content. These data show clear plateaus for lower ethane contents and mainly for water contents consistent with the formation of a single water layer. In addition, from this ensemble the structure for some of these interlaminar compositions were ana...

Formation of Core-Shell Ethane-Silver Clusters in He Droplets.

Science.gov (United States)

Loginov, Evgeny; Gomez, Luis F; Sartakov, Boris G; Vilesov, Andrey F

2017-08-17

Ethane core-silver shell clusters consisting of several thousand particles have been assembled in helium droplets upon capture of ethane molecules followed by Ag atoms. The composite clusters were studied via infrared laser spectroscopy in the range of the C-H stretching vibrations of ethane. The spectra reveal a splitting of the vibrational bands, which is ascribed to interaction with Ag. A rigorous analysis of band intensities for a varying number of trapped ethane molecules and Ag atoms indicates that the composite clusters consist of a core of ethane that is covered by relatively small Ag clusters. This metastable structure is stabilized due to fast dissipation in superfluid helium droplets of the cohesion energy of the clusters.

Gaseous products generated by radiation degradation of N,N-diethylhydroxylamine aqueous solution

International Nuclear Information System (INIS)

Wang Jinhua; Wang Shengxiu; Bao Borong; Li Zhen; Li Chun; Zheng Weifang; Zhang Shengdong

2008-01-01

In this paper, gaseous products generated by radiation degradation of N,N-diethylhydroxylamine (DEHA) in aqueous solution are studied. The results show that by 10-1000 kGy irradiation of the solution in DEHA concentration of 0.1-0.5 mol·L -1 , the gaseous products were mainly hydrogen, methane, ethane and ethene. The volume fraction of hydrogen did not change much with different concentrations of DEHA. The volume fraction of methane and ethane decreased, but that of ethene increased, with increasing DEHA concentration. The volume fraction of hydrogen, methane and ethane increased with the dose. The relationship of the volume fraction of ethene with the dose had something to do with the DEHA concentration. (authors)

Scientific conferences: A big hello to halogen bonding

Science.gov (United States)

Erdelyi, Mate

2014-09-01

Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

Reconciling Top-Down and Bottom-Up Estimates of Oil and Gas Methane Emissions in the Barnett Shale

Science.gov (United States)

Hamburg, S.

2015-12-01

Top-down approaches that use aircraft, tower, or satellite-based measurements of well-mixed air to quantify regional methane emissions have typically estimated higher emissions from the natural gas supply chain when compared to bottom-up inventories. A coordinated research campaign in October 2013 used simultaneous top-down and bottom-up approaches to quantify total and fossil methane emissions in the Barnett Shale region of Texas. Research teams have published individual results including aircraft mass-balance estimates of regional emissions and a bottom-up, 25-county region spatially-resolved inventory. This work synthesizes data from the campaign to directly compare top-down and bottom-up estimates. A new analytical approach uses statistical estimators to integrate facility emission rate distributions from unbiased and targeted high emission site datasets, which more rigorously incorporates the fat-tail of skewed distributions to estimate regional emissions of well pads, compressor stations, and processing plants. The updated spatially-resolved inventory was used to estimate total and fossil methane emissions from spatial domains that match seven individual aircraft mass balance flights. Source apportionment of top-down emissions between fossil and biogenic methane was corroborated with two independent analyses of methane and ethane ratios. Reconciling top-down and bottom-up estimates of fossil methane emissions leads to more accurate assessment of natural gas supply chain emission rates and the relative contribution of high emission sites. These results increase our confidence in our understanding of the climate impacts of natural gas relative to more carbon-intensive fossil fuels and the potential effectiveness of mitigation strategies.

Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

Science.gov (United States)

Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

2018-01-26

The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

Directory of Open Access Journals (Sweden)

Seiya Nagao

2011-12-01

Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

Breath ethane as a marker of reactive oxygen species during manipulation of diet and oxygen tension in rats.

Science.gov (United States)

Risby, T H; Jiang, L; Stoll, S; Ingram, D; Spangler, E; Heim, J; Cutler, R; Roth, G S; Rifkind, J M

1999-02-01

Breath ethane, O2 consumption, and CO2 production were analyzed in 24-mo-old female Fischer 344 rats that had been fed continuously ad libitum (AL) or restricted 30% of AL level (DR) diets since 6 wk of age. Rats were placed in a glass chamber that was first flushed with air, then with a gas mixture containing 12% O2. After equilibration, a sample of the outflow was collected in gas sampling bags for subsequent analyses of ethane and CO2. The O2 and CO2 levels were also directly monitored in the outflow of the chamber. O2 consumption and CO2 production increased for DR rats. Hypoxia decreased O2 consumption and CO2 production for the AL-fed and DR rats. These changes reflect changes in metabolic rate due to diet and PO2. A significant decrease in ethane generation was found in DR rats compared with AL-fed rats. Under normoxic conditions, breath ethane decreased from 2.20 to 1.61 pmol ethane/ml CO2. During hypoxia the levels of ethane generation increased, resulting in a DR-associated decrease in ethane from 2.60 to 1.90 pmol ethane/ml CO2. These results support the hypothesis that DR reduces the level of oxidative stress.

Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

International Nuclear Information System (INIS)

Zaera, F.; Somorhai, G.A.

1985-01-01

Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

Energy Technology Data Exchange (ETDEWEB)

Gaertner, C.A.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

2011-07-01

Ethene production is one of the most important transformations in chemical industry, given that C{sub 2}H{sub 4} serves as building block for many mass-market products. Besides conventional thermal processes like steam cracking of ethane, ethane can be produced selectively by catalytic processes. One of the classes of catalysts that have been reported in literature as active and highly selective for the oxidative dehydrogenation of ethane is that of supported molten chloride catalysts, containing an alkali chloride overlayer on a solid support. This work deals with fundamental aspects of the catalytic action in latter class of catalysts. Results from kinetic reaction studies are related to observations in detailed characterization and lead to a comprehensive mechanistic understanding. Of fundamental importance towards mechanistic insights is the oxygen storage capacity of the catalysts that has been determined by transient step experiments. (orig.)

Chemical and isotopic fractionations of natural gases during their migration. Importance of methane solubilization and diffusion during geological times; Fractionnements chimiques et isotopiques des gaz naturels lors de leur migration. Importance de la solubilisation et de la diffusion du methane au cours des temps geologiques

Energy Technology Data Exchange (ETDEWEB)

Pernaton, E

1998-09-09

Two experimental devices have been elaborated in the purpose of simulating in laboratory the solubilization of methane in water and the migration by solubilization/diffusion of some gas species (methane, ethane, propane and nitrogen) through porous media saturated with water. Significant shifts in isotopic ratios of diffused methane (carbon and hydrogen) have been observed. Those fractionations for carbon isotopes, which in most cases are characterised by a {sup 12}C-enriched diffused methane, have fundamental consequences about the interpretation of the origin of methane in sedimentary basins and, in a more general way, about the genetic characterisation of hydrocarbon gases in reservoirs. Indeed, this gives an ambiguous origin for any gas having {sup 12}C-enriched methane, two different interpretations are possible: mixing between thermogenic and bacterial hydrocarbon gases and a diffusive trend during migration. Using a diagram C2/C1 versus {delta}{sup 13}C1, we have shown that in some geological cases, these two processes, mixing and diffusion, exist and that it is possible to discern them.The chemical and isotopic compositions of natural gases do not only reflect genetic processes but are also an indication of their migration. Moreover, the experiments have shown that the gas transport by solubilization/diffusion is a potential operator of gas leakage from natural accumulations. In consequence, a numerical model of gas migration through cap rocks of reservoirs has been elaborated and will be integrated into sedimentary basin models. (author)

Exhaled ethane concentration in patients with cancer of the upper gastrointestinal tract - a proof of concept study.

Science.gov (United States)

Abela, Jo Etienne; Skeldon, Kenneth D; Stuart, Robert C; Padgett, Miles J

2009-06-01

There has been growing interest in the measurement of breath ethane as an optimal non-invasive marker of oxidative stress. High concentrations of various breath alkanes including ethane have been reported in a number of malignancies. Our aim was to investigate the use of novel laser spectroscopy for rapid reporting of exhaled ethane and to determine whether breath ethane concentration is related to a diagnosis of upper gastrointestinal malignancy. Two groups of patients were recruited. Group A (n = 20) had a histo-pathological diagnosis of either esophageal or gastric malignancy. Group B (n = 10) was made up of healthy controls. Breath samples were collected from these subjects and the ethane concentration in these samples was subsequently measured to an accuracy of 0.2 parts per billion, ppb. Group A patients had a corrected exhaled breath ethane concentration of 2.3 +/- 0.8 (mean +/- SEM) ppb. Group B patients registered a mean of 3.1 +/- 0.5 ppb. There was no statistically significant difference between the two groups (p = 0.39). In conclusion, concentrations of ethane in collected breath samples were not significantly elevated in upper gastrointestinal malignancy. The laser spectroscopy system provided a reliable and rapid turnaround for breath sample analysis.

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Science.gov (United States)

2010-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4...); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2′-[oxybis(2,1-ethanediyl oxy)]bis-, bis...

40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

Directory of Open Access Journals (Sweden)

Anon Namin

2012-01-01

Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

Directory of Open Access Journals (Sweden)

Eugenio Torres

2013-12-01

Full Text Available In this work a novel procedure of synthesis of compounds analogues to curcumin with halogens atoms in its structure is described, which can increase its solubility and biological activity. Four halogenated curcuminoids were obtained with great pharmacological interest, none of them reported in literature before. Synthesis was carried out by means of the aldol condensation assisted by microwaves of halogenated aromatic aldehydes and acetylacetona, using morpholine as basic catalyst, in absence of solvent, and the reaction just needed 1 min. The products were purified by treatment of the reaction mixture with methanol under ultrasound irradiation, followed by chromatographic column. All obtained compounds were characterized by infrared spectroscopy, nuclear magnetic resonance, quantitative elementary analysis and high resolution mass spectrometry. The RMN-1H data demonstrate in all structures of synthesized curcuminoids the enol form is the most favored.

Comparison of facility-level methane emission rates from natural gas production well pads in the Marcellus, Denver-Julesburg, and Uintah Basins

Science.gov (United States)

Omara, M.; Li, X.; Sullivan, M.; Subramanian, R.; Robinson, A. L.; Presto, A. A.

2015-12-01

The boom in shale natural gas (NG) production, brought about by advances in horizontal drilling and hydraulic fracturing, has yielded both economic benefits and concerns about environmental and climate impacts. In particular, leakages of methane from the NG supply chain could substantially increase the carbon footprint of NG, diminishing its potential role as a transition fuel between carbon intensive fossil fuels and renewable energy systems. Recent research has demonstrated significant variability in measured methane emission rates from NG production facilities within a given shale gas basin. This variability often reflect facility-specific differences in NG production capacity, facility age, utilization of emissions capture and control, and/or the level of facility inspection and maintenance. Across NG production basins, these differences in facility-level methane emission rates are likely amplified, especially if significant variability in NG composition and state emissions regulations are present. In this study, we measured methane emission rates from the NG production sector in the Marcellus Shale Basin (Pennsylvania and West Virginia), currently the largest NG production basin in the U.S., and contrast these results with those of the Denver-Julesburg (Colorado) and Uintah (Utah) shale basins. Facility-level methane emission rates were measured at 106 NG production facilities using the dual tracer flux (nitrous oxide and acetylene), Gaussian dispersion simulations, and the OTM 33A techniques. The distribution of facility-level average methane emission rate for each NG basin will be discussed, with emphasis on how variability in NG composition (i.e., ethane-to-methane ratios) and state emissions regulations impact measured methane leak rates. While the focus of this presentation will be on the comparison of methane leak rates among NG basins, the use of three complimentary top-down methane measurement techniques provides a unique opportunity to explore the

Data relative to (e, argon) and (e, ethane) interactions necessary for strong field transport calculations

International Nuclear Information System (INIS)

Florent, J.J.

1988-01-01

Collisions between electrons and argon atoms and ethane molecules are studied in order to better understand phenomena occurring at each stage of detection in gas detectors used in nuclear and high energy physics. Elastic collisions between an electron and argon, those producing an electronic excitation of the atom, and those leading to its ionisation are reviewed. For the ethane collisions, vibrational excitation is considered. Photoionisation of argon and ethane is also examined. Total or partial cross sections, and differential cross sections are presented [fr

40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

Science.gov (United States)

2010-07-01

..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

Revisiting the metathesis of 13C-monolabeled ethane

KAUST Repository

Maury, Olivier; Lefort, Laurent; Vidal, Vé ronique; Thivolle-Cazat, Jean; Basset, Jean-Marie

2010-01-01

The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction

The unique role of halogen substituents in the design of modern agrochemicals.

Science.gov (United States)

Jeschke, Peter

2010-01-01

The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

Special features of self-compensation of halogen donor action in lead telluride

International Nuclear Information System (INIS)

Kajdanov, V.I.; Nemov, S.A.; Ravich, Yu.I.; Dereza, A.Yu.

1985-01-01

Specific features of self-compensation of halogen donor action in lead telluride are investigasted. Lead telluride samples with chlorine additions (with tellurium excess) and, besides, with bromine- and iodine additions were studied in order to reveal general regularities in alloyind with all halogen donor impurities. Experimental dependences of the difference between the electron and hole concentrations (n-p) in PbTe as a function of an amount of introduced halogen impurities (Ni) are presented for samples with a maximum compensation at 295 K. General features of the n-p=f(Ni) dependence are presented for all halogens. The hypothesis on the kinetic mechanism of increasing the efficiency of self-compensation of halogen donor action in lead telluride is suggested

Spectrographic determination of traces of halogens; Dosage de traces d'halogenes par la methode spectrographique

Energy Technology Data Exchange (ETDEWEB)

Melamed, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

Hollow cathode source is employed for determining traces of halogens (fluorine - chlorine) in the uranium oxide U{sub 3}O{sub 8} qualitatively, detection of at least 40 ppm of fluorine, as alkali fluoride and 125 ppm of chlorine, is possible. (author) [French] Un tube a decharge a cathode creuse a ete utilise pour la determination spectrographique des halogenes (fluor - chlore) presentes a l'etat de traces dans un oxyde d'uranium U{sub 3}O{sub 8}. On a pu deceler qualitativement des teneurs de 40 ppm de fluor sous forme de fluorures alcalins. En ce qui concerne le chlore, la plus faible teneur decelee a ete de 125 ppm. (auteur)

Occurrence and origin of methane in groundwater in Alberta (Canada): Gas geochemical and isotopic approaches

International Nuclear Information System (INIS)

Humez, P.; Mayer, B.; Ing, J.; Nightingale, M.; Becker, V.; Kingston, A.; Akbilgic, O.; Taylor, S.

2016-01-01

To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10 mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged − 69.7 ± 11.1‰ (n = 63) in free gas and − 65.6 ± 8.9‰ (n = 26) in dissolved gas. δ"1"3C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ"1"3C values in concert with average δ"2H_C_H_4 values of − 289 ± 44‰ (n = 45) suggest that most methane was of biogenic origin predominantly generated via CO_2 reduction. This interpretation is confirmed by dryness parameters typically > 500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100–250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed. - Highlights: • Analysis of gas geochemical data from 186 monitoring wells in

Occurrence and origin of methane in groundwater in Alberta (Canada): Gas geochemical and isotopic approaches

Energy Technology Data Exchange (ETDEWEB)

Humez, P., E-mail: phumez@ucalgary.ca [Department of Geoscience, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4 (Canada); Mayer, B.; Ing, J.; Nightingale, M.; Becker, V.; Kingston, A. [Department of Geoscience, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4 (Canada); Akbilgic, O. [Department of Geoscience, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4 (Canada); UTHSC-ORNL Center for Biomedical Informatics, 910 Madison Avenue, Memphis, TN, 38104 (United States); Taylor, S. [Department of Geoscience, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4 (Canada)

2016-01-15

To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10 mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged − 69.7 ± 11.1‰ (n = 63) in free gas and − 65.6 ± 8.9‰ (n = 26) in dissolved gas. δ{sup 13}C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ{sup 13}C values in concert with average δ{sup 2}H{sub CH4} values of − 289 ± 44‰ (n = 45) suggest that most methane was of biogenic origin predominantly generated via CO{sub 2} reduction. This interpretation is confirmed by dryness parameters typically > 500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100–250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed. - Highlights: • Analysis of gas geochemical data from 186

Raman spectrum of methane in nitrogen, carbon dioxide, hydrogen, ethane, and propane environments

Science.gov (United States)

Petrov, D. V.

2018-02-01

Using binary CH4 - mixtures with varied concentrations of H2, N2, CO2, C2H6 and C3H8 and a fixed ambient pressure of 25 bar, the influence of the environment on spectral characteristics (Raman shift, half-width, peak intensity) of Q-branches of the ν1, ν2, ν3, and 2ν4 methane Raman bands are investigated. It is found that depending on the environment these bands demonstrate different changes in their Raman shifts and half-widths. It is shown that the ratios of peak intensities I(ν2)/I(ν1), I(ν3)/I(ν1) and I(2ν4)/I(ν1) are very sensitive to the environment. The Raman shifts and half-widths of CH4 bands are assumed to depend on the absolute concentration of molecules in the analyzed medium. The data obtained would be useful in Raman diagnostics of natural gas.

Tritium as an indicator of CH3 and C2H5 radicals in ethane pyrolysis

International Nuclear Information System (INIS)

Kaminski, A.M.; Sobkowski, J.

1979-01-01

The concentration of methyl and ethyl radicals formed during the pyrolysis of ethane was determined by radiochemical method. The dominant role of ethyl radicals in the pyrolysis of ethane was proved. (author)

Airborne Quantification of Methane Emissions in the San Francisco Bay Area of California

Science.gov (United States)

Guha, A.; Newman, S.; Martien, P. T.; Young, A.; Hilken, H.; Faloona, I. C.; Conley, S.

2017-12-01

The Bay Area Air Quality Management District, the San Francisco Bay Area's air quality regulatory agency, has set a goal to reduce the region's greenhouse gas (GHG) emissions 80% below 1990 levels by 2050, consistent with the State of California's climate protection goal. The Air District maintains a regional GHG emissions inventory that includes emissions estimates and projections which influence the agency's programs and regulatory activities. The Air District is currently working to better characterize methane emissions in the GHG inventory through source-specific measurements, to resolve differences between top-down regional estimates (Fairley and Fischer, 2015; Jeong et al., 2016) and the bottom-up inventory. The Air District funded and participated in a study in Fall 2016 to quantify methane emissions from a variety of sources from an instrumented Mooney aircraft. This study included 40 hours of cylindrical vertical profile flights that combined methane and wind measurements to derive mass emission rates. Simultaneous measurements of ethane provided source-apportionment between fossil-based and biological methane sources. The facilities sampled included all five refineries in the region, five landfills, two dairy farms and three wastewater treatment plants. The calculated mass emission rates were compared to bottom-up rates generated by the Air District and to those from facility reports to the US EPA as part of the mandatory GHG reporting program. Carbon dioxide emission rates from refineries are found to be similar to bottom-up estimates for all sources, supporting the efficacy of the airborne measurement methodology. However, methane emission estimates from the airborne method showed significant differences for some source categories. For example, methane emission estimates based on airborne measurements were up to an order of magnitude higher for refineries, and up to five times higher for landfills compared to bottom-up methods, suggesting significant

Study of ethane level in exhaled breath in patients with age-related macular degeneration: preliminary study.

Science.gov (United States)

Cagini, C; Giordanelli, A; Fiore, T; Giardinieri, R; Malici, B; De Medio, G E; Pelli, M A; De Bellis, F; Capodicasa, E

2011-01-01

A variety of factors have been implicated in the pathogenesis of age-related macular degeneration (ARMD), and oxidative stress plays an important role in the onset and progression of the disease. Breath ethane is now considered a specific and non-invasive test for determining and monitoring the trend of lipid peroxidation and free radical-induced damage in vivo. This test provides an index of the patients' overall oxidative stress level. We evaluated the breath ethane concentration in exhaled air in patients with advanced ARMD. In this study, we enrolled 13 patients with advanced ARMD and a control group, and a breath analysis was carried out by gas chromatography. The mean ethane level in the ARMD patients was 0.82 ± 0.93 nmol/l (range: 0.01-2.7 nmol/l) and the mean ethane value in the control group was 0.12 ± 0.02 nmol/l (range: 0.08-0.16 nmol/l). The difference between the values of the 2 groups was statistically significant (p ethane levels are higher in most patients with ARMD. The breath ethane test could thus be a useful method for evaluating the level of oxidative stress in patients with ARMD. To our knowledge, there are no data on this type of analysis applied to ARMD. Copyright © 2011 S. Karger AG, Basel.

High-performance carbon molecular sieve membranes for ethylene/ethane separation derived from an intrinsically microporous polyimide

KAUST Repository

Salinas, Octavio

2015-11-18

An intrinsically microporous polymer with hydroxyl functionalities, PIM-6FDA-OH, was used as a precursor for various types of carbon molecular sieve (CMS) membranes for ethylene/ethane separation. The pristine polyimide films were heated under controlled N2 atmosphere at different stages from 500 to 800 °C. All CMS samples carbonized above 600 °C surpassed the polymeric ethylene/ethane upper bound. Pure-gas selectivity reached 17.5 for the CMS carbonized at 800 °C with an ethylene permeability of about 10 Barrer at 2 bar and 35 °C, becoming the most selective CMS for ethylene/ethane separation reported to date. As expected, gravimetric sorption experiments showed that all CMS membranes had ethylene/ethane solubility selectivities close to one. The permselectivity increased with increasing pyrolysis temperature due to densification of the micropores in the CMS membranes, leading to enhanced diffusivity selectivity. Mixed-gas tests with a binary 50:50 v/v ethylene/ethane feed showed a decrease in selectivity from 14 to 8.3 as the total feed pressure was increased from 4 to 20 bar. The selectivity drop under mixed-gas conditions was attributed to non-ideal effects: (i) Competitive sorption that reduced the permeability of ethylene and (ii) dilation of the CMS that resulted in an increase in the ethane permeability.

Halogenated organic compounds in archived whale oil: A pre-industrial record

International Nuclear Information System (INIS)

Teuten, Emma L.; Reddy, Christopher M.

2007-01-01

To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s

Halogenated organic compounds in archived whale oil: A pre-industrial record

Energy Technology Data Exchange (ETDEWEB)

Teuten, Emma L. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: emma.teuten@plymouth.ac.uk; Reddy, Christopher M. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: creddy@whoi.edu

2007-02-15

To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s.

Effect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage

KAUST Repository

Belmabkhout, Youssef

2014-01-01

Equilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1, correspondingly dubbed tbo-MOF-1), which were developed via the supermolecular building layer (SBL) pillaring strategy. Specifically, tbo-MOF-2 and its isoreticular, functionalized analogue, tbo-MOF-2-{CH2O[Ph(CO2H)2]}2 (or tbo-MOF-3), which is characterized by pendant isophthalic acid moieties freely pointing into the cavities, were evaluated on the basis of potential use in methane storage and C2+/CH4 separation. The parent, tbo-MOF-2, showed high gravimetric and volumetric CH4 uptake, close to the U.S. Department of Energy (DOE) target for methane storage at 35 bar and room temperature. Though the presence of the pendant isophthalic acid moiety in the analogous compound, tbo-MOF-3, led to a decrease in total CH4 uptake, due mainly to the reduced size of the cavities, interestingly, it increased the affinity of the SBL-based tbo-MOF platform for propane, propene, ethane, and ethylene at low pressures compared with CH4, due additionally to the enhanced interactions of the highly polarizable light hydrocarbons with the isophthalic acid moiety. Using Ideal Adsorption Solution Theory (IAST), the predicted mixture adsorption equilibria for the C3H8/CH4, C3H6/CH4, C2H6/CH4, C2H4/CH4, and C3H8/CO2 systems showed high adsorption selectivity for C2+ over methane for tbo-MOF-3 compared with tbo-MOF-2. The high working storage capacity of tbo-MOF-2 and the high affinity of tbo-MOF-3 for C2+ over CH4 and CO2 make tbo-MOF an ideal platform for studies in gas storage and separation.

Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

Science.gov (United States)

Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

2018-05-01

The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

Science.gov (United States)

Rissanen, Kari; Haukka, Matti

2015-01-01

The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

Distribution of MEG and methanol in well-defined hydrocarbon and water systems: Experimental measurement and modeling using the CPA EoS

DEFF Research Database (Denmark)

Riaz, Muhammad; Yussuf, Mustafe A.; Kontogeorgis, Georgios

2013-01-01

+ water. These data are satisfactorily correlated (binaries) and predicted (ternaries) using Cubic Plus Association (CPA) equation of state (EoS). CPA is also applied to binary LLE of aromatic hydrocarbon + water and VLE of methane + methanol. Finally the distribution of water and inhibitors (methanol...... and MEG) in various phases is modeled using CPA. The hydrocarbon phase consists of mixture-1 (methane, ethane, n-butane) or mixture-2 (methane, ethane, propane, n-butane, n-heptane, toluene and n-decane). CPA can satisfactorily predict the water content in the gas phase of the multicomponent systems...

Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

International Nuclear Information System (INIS)

Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

1977-01-01

Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

Structural optimization of interpenetrated pillared-layer coordination polymers for ethylene/ethane separation.

Science.gov (United States)

Kishida, Keisuke; Horike, Satoshi; Watanabe, Yoshihiro; Tahara, Mina; Inubushi, Yasutaka; Kitagawa, Susumu

2014-06-01

With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared-layer-type porous coordination polymers with double interpenetration, [Zn2(tp)2(bpy)]n (1), [Zn2(fm)2(bpe)]n (2), [Zn2(fm)2(bpa)]n (3), and [Zn2(fm)2(bpy)]n (4) (tp = terephthalate, bpy = 4,4'-bipyridyl, fm = fumarate, bpe = 1,2-di(4-pyridyl)ethylene and bpa = 1,2-di(4-pyridyl)ethane). It was found that 4, which contains the narrowest pores of all of these compounds, exhibited ethylene-selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

Science.gov (United States)

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-04-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

DEFF Research Database (Denmark)

Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

2002-01-01

fischeri overproduced in Escherichia coli. Whilst a stable interaction between the algal metabolite and the bacterial protein was not found, it was noted by Western analysis that the half-life of the protein is reduced up to 100-fold in the presence of halogenated furanones. This suggests that halogenated...... that the reduction in LuxR concentration is the mechanism by which furanones control expression of AHL-dependent phenotypes. The mode of action by which halogenated furanones reduce cellular concentrations of the LuxR protein remains to be characterized....

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

Science.gov (United States)

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

Thermal behavior of halogenated imidebismaleimide resins

International Nuclear Information System (INIS)

Mohammad, A.; Al-Halim, N.Z.

1995-01-01

Several new poly-halogenated malecimides, bismaleimides and therir copoly resins were synthessised thermally from their corresponding amic acids. The synthesis was accomplished by two way method (amic acid-polimide) instead of the well-known three way method (amic acid-imide-polyimide). Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The effect of halogen substituent, especially in the ortho postion, is clear in the imidization proces, while polymerization proceeds almost equally in all systems. Thermal properties of homo and copolymers were correlated with their chemical structures. (author). 15 refs., 4

Regularities of catalytic reactions of hydrogen, ethane and ethylene with elementary sulfur

International Nuclear Information System (INIS)

Zazhigalov, V.A.

1978-01-01

Shown is the decisive role of metal-sulfur bond stability for activity determination of metal sulfides (WS 2 , MoS 2 , CdS) in interaction reactions of elementary sulfur and hydrogen, ethane and ethylene. Found is the regularity of changing the relative reactiveness of the given substances and a conclusion is made about uniformity of the investigated catalyst processes. The results of hydrogen, ethane and ethylene oxidation by oxygen and sulfur are compared, the semilarity of these processes being pointed out

Development of non-halogen cables for nuclear power stations

Energy Technology Data Exchange (ETDEWEB)

Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao (Hitachi Cable, Ltd., Tokyo (Japan))

1983-12-01

The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables.

Development of non-halogen cables for nuclear power stations

International Nuclear Information System (INIS)

Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao

1983-01-01

The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables. (Yoshitake, I.)

Electron mobility in supercritical ethane as a function of density and temperature

International Nuclear Information System (INIS)

Nishikawa, M.; Holroyd, R.A.; Sowada, U.

1980-01-01

The electron mobility is reported for ethane as a function of density at various temperatures above T/sub c/. The high pressure cell used permits measurements to 200 atm. Our analysis shows that theory is consistent with the ethane mobility results at low and intermediate densities. At densities less than 1 x 10 21 molecules/cm 3 electrons are scattered by isolated ethane molecules and the Lorentz equation is valid. At intermediate densities, μ/sub e/ correlates with the square of the velocity of sound, indicating that in dense fluids the adiabatic compressibility must be included. The data are consistent with a modified Cohen--Lekner equation, and the minimum in μ/sub e/N observed at densities just below d/sub c/ is qualitatively accounted for by changes in the adiabatic compressibility. Thus the concept of quasilocalization, suggested by others to qualitatively explain such minima, is unnecessary here. At higher densities an additional, unspecified, scattering mechanism becomes important

Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

KAUST Repository

Takanabe, Kazuhiro

2016-08-21

The dehydrogenation of ethane to ethylene in the presence of oxygen and water was conducted using Na2WO4/SiO2 catalyst at high temperatures. At 923 K, the conversion rate without water was proportional to ethane pressure and a half order of oxygen pressure, consistent with a kinetically relevant step where an ethane molecule is activated with dissociated oxygen on the surface. When water was present, the ethane conversion rate was drastically enhanced. An additional term in the rate expression was proportional to a quarter of the oxygen pressure and a half order of the water pressure. This mechanism is consistent with the quasi-equilibrated OH radical formation with subsequent ethane activation. The attainable yield can be accurately described by taking the water contribution into consideration. At high conversion levels at 1073 K, the C2H4 yield exceeded 60% in a single-pass conversion. The C2H4 selectivity was almost insensitive to the C2H6 and O2 pressures. © 2016 American Institute of Chemical Engineers.

Process for reducing halogen impurities in oil products

Energy Technology Data Exchange (ETDEWEB)

Basler, F.

1990-08-14

Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

Directory of Open Access Journals (Sweden)

Yi Yang

2017-10-01

Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

Revisiting the metathesis of 13C-monolabeled ethane

KAUST Repository

Maury, Olivier

2010-12-13

The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction scheme combining both processes. © 2010 American Chemical Society.

Methane as a biomarker in the search for extraterrestrial life: Lessons learned from Mars analog hypersaline environments

Science.gov (United States)

Bebout, B.; Tazaz, A.; Kelley, C. A.; Poole, J. A.; Davila, A.; Chanton, J.

2010-12-01

Methane released from discrete regions on Mars, together with previous reports of methane determined with ground-based telescopes, has revived the possibility of past or even extant life near the surface on Mars, since 90% of the methane on Earth has a biological origin. This intriguing possibility is supported by the abundant evidence of large bodies of liquid water, and therefore of conditions conducive to the origin of life, early in the planet's history. The detection and analysis of methane is at the core of NASA’s strategies to search for life in the solar system, and on extrasolar planets. Because methane is also produced abiotically, it is important to generate criteria to unambiguously assess biogenicity. The stable carbon and hydrogen isotopic signature of methane, as well as its ratio to other low molecular weight hydrocarbons (the methane/(ethane + propane) ratio: C1/(C2 + C3)), has been suggested to be diagnostic for biogenic methane. We report measurements of the concentrations and stable isotopic signature of methane from hypersaline environments. We focus on hypersaline environments because spectrometers orbiting Mars have detected widespread chloride bearing deposits resembling salt flats. Other evaporitic minerals, e.g., sulfates, are also abundant in several regions, including those studied by the Mars Exploration Rovers. The presence of evaporitic minerals, together with the known evolution of the Martian climate, from warmer and wetter to cold and hyper-arid, suggest that evaporitic and hypersaline environments were common in the past. Hypersaline environments examined to date include salt ponds located in Baja California, the San Francisco Bay, and the Atacama Desert. Methane was found in gas produced both in the sediments, and in gypsum- and halite-hosted (endolithic) microbial communities. Maximum methane concentrations were as high as 40% by volume. The methane carbon isotopic (δ13C) composition showed a wide range of values, from about

Assessing the Efficacy of the Aerobic Methanotrophic Biofilter in Methane Hydrate Environments

Energy Technology Data Exchange (ETDEWEB)

Valentine, David

2012-09-30

process as a biofilter by studying the distribution of methane oxidation and disposition of methanotrophic populations in the Pacific Ocean. We investigated several environments including the basins offshore California, the continental margin off Central America, and the shallow waters around gas seeps. We succeeded in identifying the distributions of activity in these environments, identified potential physical and chemical controls on methanotrophic activity, we further revealed details about the methanotrophic communities active in these settings, and we developed new approaches to study methanotrophic communities. These findings should improve our capacity to predict the methanotrophic response in ocean waters, and further our ability to generate specific hypotheses as to the ecology and efficacy of pelagic methanotrophic communites. The discharge of methane and other hydrocarbons to Gulf of Mexico that followed the sinking of the Deepwater Horizon provided a unique opportunity to study the methanotorphic biofilter in the deep ocean environment. We set out to understand the consumption of methane and the bloom of methanotrophs resulting from this event, as a window into the regional scale release of gas hydrate under rapid warming scenarios. We found that other hydrocarbon gases, notably propane and ethane, were preferred for consumption over methane, but that methane consumption accelerated rapidly and drove the depletion of methane within a matter of months after initial release. These results revealed the identity of the responsible community, and point to the importance of the seed population in determining the rate at which a methanotrophic community is able to respond to an input of methane. Collectively, these results provide a significant advance in our understanding of the marine methanotrohic biofilter, and further provide direction and context for future investigations of this important phenomenon. This project has resulted in fourteen publications to date

First-principles studies on the effects of halogen adsorption on monolayer antimony.

Science.gov (United States)

Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

2017-09-27

Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

A five year record of high-frequency in situ measurements of non-methane hydrocarbons at Mace Head, Ireland

Directory of Open Access Journals (Sweden)

A. Grant

2011-05-01

Full Text Available Continuous high-frequency in situ measurements of a range of non-methane hydrocarbons have been made at Mace Head since January 2005. Mace Head is a background Northern Hemispheric site situated on the eastern edge of the Atlantic. Five year measurements (2005–2009 of six C₂–C₅ non-methane hydrocarbons have been separated into baseline Northern Hemispheric and European polluted air masses, among other sectors. Seasonal cycles in baseline Northern Hemispheric air masses and European polluted air masses arriving at Mace Head have been studied. Baseline air masses show a broad summer minima between June and September for shorter lived species, longer lived species show summer minima in July/August. All species displayed a winter maxima in February. European air masses showed baseline elevated mole fractions for all non-methane hydrocarbons. Largest elevations (of up to 360 ppt for ethane maxima from baseline data were observed in winter maxima, with smaller elevations observed during the summer. Analysis of temporal trends using the Mann-Kendall test showed small (<6 % yr⁻¹ but statistically significant decreases in the butanes and i-pentane between 2005 and 2009 in European air. No significant trends were found for any species in baseline air.

Geometrical changes during the internal rotation in ethane

NARCIS (Netherlands)

Monkhorst, H. J.

Theoretical and experimental indications are presented that the predominant geometrical change during the internal rotation in ethane is a stretching of the CC bond by about 1%. going from the staggered to the eclipsed conformation. This suggests that the rotation barrier is primarily caused by the

Ethene/ethane separation by the MOF membrane ZIF-8: Molecular correlation of permeation, adsorption, diffusion

NARCIS (Netherlands)

Bux, H.; Chmelik, C.; Krishna, R.; Caro, J.

2011-01-01

The newly developed MOF membrane ZIF-8 separates an equimolar ethene/ethane mixture at room temperature for 1 and 6 bar feed pressure, respectively, with a selectivity of 2.8 and 2.4. Independent sorption uptake studies of an ethene/ethane mixture on a big ZIF-8 single crystal by IR microscopy

Study of straw chamber lifetime with argon ethane

International Nuclear Information System (INIS)

Adler, J.; Bolton, T.; Bunnell, K.; Cheu, E.; Grab, C.; Mazaheri, G.; Odian, A.; Pitman, D.; Stockhausen, W.; Toki, W.; Wadley, W.; Wood, C.; Mir, R.

1989-01-01

We present detailed laboratory measurements of the lifetime of a small test chamber, simulating the Mark III straw vertex chamber conditions. The tests were carried out with an argon-ethane 50/50 gas mixture at 3 atm absolute pressure and 3.9 kV applied to the wires. After the accumulation of ≅ 0.02 C/cm on a single straw, continuous discharges began. The addition of alcohol or water vapor to the gas mixture was found to extend the lifetime of the straws. Continuous flow of the gas mixture with water vapor through the straws prolonged the lifetime significantly. We present results on the effects of changing the gas mixture inside the straws at regular time intervals. Adding a small percentage of water vapor to the argon-ethane gas and flowing the gas mixture in the straws can improve the lifetime by more than an order of magnitude. An accumulated charge of 1.0 C/cm on a single straw has been obtained. (orig.)

Global atmospheric concentrations and source strength of ethane

Science.gov (United States)

Blake, D. R.; Rowland, F. S.

1986-01-01

A study of the variation in ethane (C2H6) concentration between northern and southern latitudes over three years is presented together with a new estimate of its source strength. Ethane concentrations vary from 0.07 to 2 p.p.b.v. (parts per billion by volume) in air samples collected in remote surface locations in the Pacific (latitude 71 N-47 S) in all four seasons between September 1984 and June 1985. The variations are consistent with southerly transport from sources located chiefly in the Northern Hemisphere, further modified by seasonal variations in the strength of the reaction of C2H6 with OH radicals. These global data can be combined with concurrent data for CH4 and the laboratory reaction rates of each with OH to provide an estimate of three months as the average atmospheric lifetime for C2H6 and 13 + or - 3 Mtons for its annual atmospheric release.

Halogenation dictates the architecture of amyloid peptide nanostructures.

Science.gov (United States)

Pizzi, Andrea; Pigliacelli, Claudia; Gori, Alessandro; Nonappa; Ikkala, Olli; Demitri, Nicola; Terraneo, Giancarlo; Castelletto, Valeria; Hamley, Ian W; Baldelli Bombelli, Francesca; Metrangolo, Pierangelo

2017-07-20

Amyloid peptides yield a plethora of interesting nanostructures though difficult to control. Here we report that depending on the number, position, and nature of the halogen atoms introduced into either one or both phenylalanine benzene rings of the amyloid β peptide-derived core-sequence KLVFF, four different architectures were obtained in a controlled manner. Our findings demonstrate that halogenation may develop as a general strategy to engineer amyloidal peptide self-assembly and obtain new amyloidal nanostructures.

Synthesis and characterization of conventional and mesoporous Ga-MFI for ethane dehydrogenation

DEFF Research Database (Denmark)

Leth, Karen Thrane; Rovik, Anne Krogh; Holm, Martin Spangsberg

2008-01-01

difference being the morphology of the crystals. The catalytic properties of the samples were tested in ethane dehydrogenation at 823 K and at atmospheric pressure. The two Ga-MFI samples differ greatly in conversion of ethane, as a result of their difference in porosity, and it is found that the conversion...... is reported for tetrahedral Ga incorporated in the MFI structure and it is shown that absorbed water molecules have an important impact on the Ga-71 electric field gradients and thereby on the quantitative evaluation of the Ga-71 MAS NMR intensities....

Theoretical and experimental study of the vibrational excitations in ethane monolayers adsorbed on graphite (0001) surfaces

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Taub, H.

1987-01-01

The collective vibrational excitations of two different crystalline monolayer phases of ethane (C2H6) adsorbed on the graphite (0001) surface have been investigated theoretically and experimentally. The monolayer phases studied are the commensurate 7/8 ×4 structure in which the ethane molecules lie...

Carbon and hydrogen isotopic composition of methane and C2+ alkanes in electrical spark discharge: implications for identifying sources of hydrocarbons in terrestrial and extraterrestrial settings.

Science.gov (United States)

Telling, Jon; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2013-05-01

The low-molecular-weight alkanes--methane, ethane, propane, and butane--are found in a wide range of terrestrial and extraterrestrial settings. The development of robust criteria for distinguishing abiogenic from biogenic alkanes is essential for current investigations of Mars' atmosphere and for future exobiology missions to other planets and moons. Here, we show that alkanes synthesized during gas-phase radical recombination reactions in electrical discharge experiments have values of δ(2)H(methane)>δ(2)H(ethane)>δ(2)H(propane), similar to those of the carbon isotopes. The distribution of hydrogen isotopes in gas-phase radical reactions is likely due to kinetic fractionations either (i) from the preferential incorporation of (1)H into longer-chain alkanes due to the more rapid rate of collisions of the smaller (1)H-containing molecules or (ii) by secondary ion effects. Similar δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns may be expected in a range of extraterrestrial environments where gas-phase radical reactions dominate, including interstellar space, the atmosphere and liquid hydrocarbon lakes of Saturn's moon Titan, and the outer atmospheres of Jupiter, Saturn, Neptune, and Uranus. Radical recombination reactions at high temperatures and pressures may provide an explanation for the combined reversed δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns of terrestrial alkanes documented at a number of high-temperature/pressure crustal sites.

Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts

International Nuclear Information System (INIS)

Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

2015-01-01

Halogenated nitrogenous disinfection byproducts (N-DBPs) raise concerns regarding their mutagenicity and carcinogenicity threatening public health. However, environmental consequence of their mutagenicity has received less attention. In this study, the effect of halogenated N-DBPs on bacterial antibiotic resistance (BAR) was investigated. After exposure to bromoacetamide (BAcAm), trichloroacetonitrile (TCAN) or tribromonitromethane (TBNM), the resistance of Pseudomonas aeruginosa PAO1 to both individual and multiple antibiotics (ciprofloxacin, gentamicin, polymyxin B, rifampin, tetracycline, ciprofloxacin + gentamicin and ciprofloxacin + tetracycline) was increased, which was predominantly ascribed to the overexpression of efflux pumps. The mechanism of this effect was demonstrated to be mutagenesis through sequencing and analyzing antibiotic resistance genes. The same induction phenomena also appeared in Escherichia coli, suggesting this effect may be universal to waterborne pathogens. Therefore, more attention should be given to halogenated N-DBPs, as they could increase not only genotoxicological risks but also epidemiological risks of drinking water. - Highlights: • The halogenated N-DBPs could induce bacterial antibiotic resistance. • Both individual and multiple resistances could be induced. • Efflux mechanism played an important role in the induced antibiotic resistance. • The halogenated N-DBPs induced bacterial antibiotic resistance via mutagenesis. • Effects of N-DBPs on antibiotic resistance may be universal to waterborne pathogens. - Halogenated N-DBPs could increase antibiotic resistance, even multidrug resistance via mutagenesis, contributing to the enrichment of antibiotic resistant bacteria in drinking water

Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

Science.gov (United States)

Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli

2018-03-01

The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

Infrared absorption cross sections for ethane (C2H6) in the 3 μm region

International Nuclear Information System (INIS)

Harrison, Jeremy J.; Allen, Nicholas D.C.; Bernath, Peter F.

2010-01-01

Infrared absorption cross sections for ethane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125/HR). Results are presented for pure ethane gas from spectra recorded at 0.004 cm -1 resolution and for mixtures with dry synthetic air from spectra obtained at 0.015 cm -1 resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using three ethane spectra (recorded at 278, 293, and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.

Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo

2014-06-01

The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

Detection of CO and Ethane in Comet 21P/Giacobini-Zinner: Evidence for Variable Chemistry in the Outer Solar Nebula.

Science.gov (United States)

Mumma; DiSanti; Dello Russo N; Magee-Sauer; Rettig

2000-03-10

Ethane and carbon monoxide were detected in a short-period comet of probable Kuiper Belt origin. Ethane is substantially less abundant compared with Hyakutake and Hale-Bopp, two comets from the giant-planet region of the solar nebula, suggesting a heliocentric gradient in ethane in precometary ices. It is argued that processing by X-rays from the young Sun may be responsible.

Qualitative and quantitative analysis of light hydrocarbons produced by radiation degradation of N, N-dimethyl hydroxylamine

International Nuclear Information System (INIS)

Wang Jinhua; Bao Borong; Wu Minghong; Sun Xilian; Zhang Xianye; Hu Jingxin; Ye Guoan

2004-01-01

This paper reports the qualitative and quantitative analysis of light hydrocarbons produced by radiation degradation of N, N-dimethyl hydroxylamine. These analyses were performed on the gas chromatograph, in which porous layer open tubular column coated with aluminum oxide and flame-ionization detector are used. For the doses between 10 and 1000 kGy, the light hydrocarbons produced by radiation degradation of N,N-dimethyl hydroxylamine are methane, ethane, ethene, propane, propene and n-butane. When the concentration of N,N-dimethyl hydroxylamine is 0.2 mol/L, the volume fraction of methane is (9.996-247.5) x 10 -6 , the volume fraction of ethane, propane and n-butane is lower and that of ethene and propene is much lower. With the increase of dose the volume fraction of methane is increased but the volume fraction of ethane, ethene, propane, propene and n-butane is not obviously changed. (authors)

Experimental simulations of ethylene evaporites on Titan

Science.gov (United States)

Czaplinski, E.; Farnsworth, K.; Singh, S.; Chevrier, V.

2017-12-01

Titan has an abundance of lakes and seas, as identified by the Cassini spacecraft. Major components of these liquid bodies include methane (CH4) and ethane (C2H6), however minor constituents are also thought to exist (e.g. ethylene (C2H4)). As the lakes and seas evaporate, 5-μm-bright deposits, resembling evaporite deposits on Earth, are left behind in a "bathtub ring" fashion. Previous studies include models of evaporites, and observations of the 5-μm-bright regions, but the community is still lacking a complete suite of experimental evaporite studies. In this study, we experimentally investigate evaporites in order to determine their composition and how they affect infrared spectra during the evaporation process. The University of Arkansas owns a specialized chamber that simulates the surface conditions of Titan ( 90 K and 1.5 bar). Gaseous hydrocarbons are condensed within the chamber and analyzed with Fourier Transform Infrared (FTIR) Spectroscopy and band depth calculations. In this study, three types of experiments were performed: ethane/ethylene, methane/ethylene, and methane/ethane/ethylene. For these experiments, methane was the only species that readily evaporated at Titan conditions (due to its high volatility), while ethane, being the more stable solvent, did not readily evaporate. Therefore, we will present spectral results of ethylene evaporite formation within these mixtures. Our results imply that evaporite formation is strongly dependent on the composition of the solvent. The north polar lakes of Titan are predicted to be methane-rich, indicating that they may be more likely to form evaporites. Alternatively, Ontario Lacus, a south polar lake, is predominately composed of ethane, which may make it more difficult to form evaporites. As we continue to study Titan's mysterious lakes and seas, we hope to draw insights on their exact composition, conditions for evaporite formation, habitability potential, and comparing Titan to prebiotic Earth.

Excess electron mobility in ethane. Density, temperature, and electric field effects

International Nuclear Information System (INIS)

Doeldissen, W.; Schmidt, W.F.; Bakale, G.

1980-01-01

The excess electron mobility in liquid ethane was measured under orthobaric conditions as a function of temperature and electric field strength up to the critical temperature at 305.33 K. The low field mobility was found to rise strongly with temperature and exhibits a maximum value of 44 cm 2 V -1 s -1 at 2 0 below the critical temperature. At temperatures above 260 K the electron drift velocity shows a sublinear field dependence at high values of the electric field strength. These observations lead to the supposition that in liquid ethane a transition from transport via localized states to transport in extended states occurs. Measurements were also performed in fluid ethane at densities from 2.4 to 12.45 mol L -1 and temperatures from 290 to 340 K. On isochores in the vicinity of the critical density, an increase of the low field mobility with temperature was observed. This effect was found to disappear both at low (rho = 2.4 mol L -1 ) and high densities (rho greater than or equal to 9.2 mol L -1 ). In this density range, a sublinear field dependence of the drift velocities at high field strengths was noted. The critical velocity associated with the appearance of hot electrons was observed to decrease with higher densities indicating a smaller fractional energy transfer in electron molecule collisions. A compilation of electron mobilities in gaseous and liquid ethane shows that, up to densitiesof rho = 9.5 mol L -1 , μ proportional to n -1 is fulfilled if temperature effects are ignored. At intermediate densities, 9 mol L -1 -1 , a density dependence of μ proportional to rho -5 is found followed by a stronger mobility decrease toward the triple point. Positive ion mobilities measured under orthobaric conditions followed Walden's rule

The origin of the methane in deep aquifers of the Pannonian Basin

International Nuclear Information System (INIS)

Futo, I.; Svingor, E.; Szanto, Zs.

2004-01-01

sulfate reduction. In about one third of the waters the methane δD values are more negative than - 278%. These samples contain a relatively high amount of sulfate (35-45 mg/l) and do not show a direct relationship between the H isotope ratio of the methane and that of the water. In this waters sulfate reduction was inhibited by some unknown mechanism and, with continuing burial, the corresponding aquifers became sites of intensive bacterial acetogenesis and subsequent fermentation of the acetate to methane in the depth interval of about 600- 1000 m at temperatures of about 40-60 deg C. The effectiveness of the acetate fermentation was highly variable. During the last glacial period meteoric waters invaded some of the corresponding aquifers, reducing drastically the concentrations of methane. The minor amounts of ethane and other heavy hydrocarbon gases are mostly of early thermogenic origin. The contribution of early thermogenic methane is too slight to alter significantly the very negative, bacterial C isotopic signature of the methane present in the waters. Our results show that deep, hot acetate fermentation and early thermal gas generation can occur closely in space and time and even partly overlap. (author)

Methane Leakage from Oil & Gas Operations. What have we learned from recent studies in the U.S.?

Science.gov (United States)

Zavala-Araiza, Daniel; Hamburg, Steven

2016-04-01

Methane, the principal component of natural gas, is a powerful greenhouse gas. Methane losses from the natural gas supply chain erode the climate benefits of fuel switching to natural gas from other fossil fuels, reducing or eliminating them for several decades or longer. Global data on methane emissions from the oil and gas sector is uncertain and as a consequence, measuring and characterizing methane emissions is critical to the design of effective mitigation strategies. In this work, we synthesize lessons learned from dozens of U.S. studies that characterized methane emissions along each stage of the natural gas supply chain. These results are relevant to the design of methane measurement campaigns outside the U.S. A recurring theme in the research conducted in the U.S. is that public emissions inventories (e.g., The U.S. Environmental Protection Agency's National Greenhouse gas Inventory) tend to underestimate emissions for two key reasons: (1) use of non-representative emission factors and (2) inaccurate activity data (incomplete counts of facilities and equipment). Similarly, the accuracy of emission factors and the effectiveness of mitigation strategies are heavily affected by the existence of low-probability, unpredictable high emitters-which have been observed all along the supply chain- and are spatiotemporally variable. We conducted a coordinated campaign to measure methane emissions in a major gas producing region of the U.S. (Barnett Shale region of Texas) using a diversity of approaches. As part of this study we identified methods for effective quantification of regional fossil methane emissions using atmospheric data (through replicate mass balance flights and source apportionment using methane to ethane ratios) as well as how to build an accurate inventory that includes a statistical estimator that more rigorously captures the magnitude and frequency of high emitters. We found agreement between large-scale atmospheric sampling estimates and source

Non-equilibrium plasma reactor for natrual gas processing

International Nuclear Information System (INIS)

Shair, F.H.; Ravimohan, A.L.

1974-01-01

A non-equilibrium plasma reactor for natural gas processing into ethane and ethylene comprising means of producing a non-equilibrium chemical plasma wherein selective conversion of the methane in natural gas to desired products of ethane and ethylene at a pre-determined ethane/ethylene ratio in the chemical process may be intimately controlled and optimized at a high electrical power efficiency rate by mixing with a recycling gas inert to the chemical process such as argon, helium, or hydrogen, reducing the residence time of the methane in the chemical plasma, selecting the gas pressure in the chemical plasma from a wide range of pressures, and utilizing pulsed electrical discharge producing the chemical plasma. (author)

High Resolution NMR Studies of Encapsulated Proteins In Liquid Ethane

Science.gov (United States)

Peterson, Ronald W.; Lefebvre, Brian G.; Wand, A. Joshua

2005-01-01

Many of the difficulties presented by large, aggregation-prone, and membrane proteins to modern solution NMR spectroscopy can be alleviated by actively seeking to increase the effective rate of molecular reorientation. An emerging approach involves encapsulating the protein of interest within the protective shell of a reverse micelle, and dissolving the resulting particle in a low viscosity fluid, such as the short chain alkanes. Here we present the encapsulation of proteins with high structural fidelity within reverse micelles dissolved in liquid ethane. The addition of appropriate co-surfactants can significantly reduce the pressure required for successful encapsulation. At these reduced pressures, the viscosity of the ethane solution is low enough to provide sufficiently rapid molecular reorientation to significantly lengthen the spin-spin NMR relaxation times of the encapsulated protein. PMID:16028922

Fragrance material review on 1-(3,3-dimethylcyclohexyl)ethan-1-one.

Science.gov (United States)

Scognamiglio, J; Letizia, C S; Api, A M

2013-12-01

A Toxicologic and Dermatologic review of 1-(3,3-dimethylcyclohexyl)ethan-1-one when used as a fragrance ingredient is presented. 1-(3,3-Dimethylcyclohexyl)ethan-1-one is a member of the fragrance structural group Alkyl Cyclic Ketones. These fragrances can be described as being composed of an alkyl, R1, and various substituted and bicyclic saturated or unsaturated cyclic hydrocarbons, R2, in which one of the rings may include up to 12 carbons. Alternatively, R2 may be a carbon bridge of C2-C4 carbon chain length between the ketone and cyclic hydrocarbon. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 1-(3,3-dimethylcyclohexyl)ethan-1-one were evaluated then summarized and includes physical properties, skin irritation, mucous membrane (eye) irritation, skin sensitization, and genotoxicity data. A safety assessment of the entire Alkyl Cyclic Ketones will be published simultaneously with this document; please refer to Belsito et al., 2013(1) for an overall assessment of the safe use of this material and all Alkyl Cyclic Ketones in fragrances. Copyright © 2013 Elsevier Ltd. All rights reserved.

Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

KAUST Repository

Takanabe, Kazuhiro; Shahid, Salman

2016-01-01

The dehydrogenation of ethane to ethylene in the presence of oxygen and water was conducted using Na2WO4/SiO2 catalyst at high temperatures. At 923 K, the conversion rate without water was proportional to ethane pressure and a half order of oxygen

Double C-H activation of ethane by metal-free SO2*+ radical cations.

Science.gov (United States)

de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

2010-06-01

The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

Directory of Open Access Journals (Sweden)

Naoya Usuki

2017-12-01

Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

International Nuclear Information System (INIS)

Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue; Jin Weijun

2012-01-01

Highlights: ► Halogen bonding (XB) is firstly utilised in solid phase extraction. ► The perfluorinated iodine alkanes can be extracted by C-I⋯Cl − halogen bonding. ► The C-I⋯Cl − halogen bond is well characterised by spectroscopy methods. ► The analytes with strong halogen-bonding abilities can be selectively extracted. - Abstract: For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19 F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the C-I⋯Cl − halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL −1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl − . The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g −1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g −1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

CERN Document Server

MacKinlay, Alistair F; Whillock, M J

1989-01-01

This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

International Nuclear Information System (INIS)

McKinlay, A.F.; Whillock, M.J.; Meulemans, C.C.E.

1989-07-01

This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard. (author)

Carbon dioxide reforming of methane by atmospheric pressure pulsed glow discharge: The effect of pulse compression

International Nuclear Information System (INIS)

Ghorbanzadeh, A.; Modarresi, H.

2006-01-01

Methane reforming by carbon dioxide in atmospheric pressure pulsed glow discharge was examined. The pulse duration of plasma was compressed to ∼50 ns or lower. This compression allowed working at higher frequencies, more than 3 k Hz, without glow to arc transition. The main outlet gases were synthetic gases (H 2 , CO) and C 2 (ethylene, ethane, and acetylene) products. At equal reactants proportion CO 2 /CH 4 =1, about 42 p ercent o f plasma energy went to chemical dissociation while reactant conversions were relatively high, i.e. near 55 p ercent % (CH 4 ) and 42 p ercent ( CO 2 ). At this point, the energy expenditure was less than 3.8 eV per each converted molecule. The reactor energy performance even gets better at higher CO 2 /CH 4 proportions. At CO 2 /CH 4 =5, The conversions of about 65 p ercent a nd 45 p ercent w ere obtained for methane and carbon dioxide respectively, while energy efficiency reached near 45 p ercent . It is discussed that high nonequilibrium state of vibrational energy at short pulses, especially in carbon dioxide, leads to this improvement.

Lithium/magnesium oxide catalyst and method of making

Energy Technology Data Exchange (ETDEWEB)

Lunsford, J.H.; Hinson, P.G.

1991-07-16

This patent describes a method for preparing a catalyst which is effective for converting methane to ethane and ethylene. It comprises mixing a solution of a magnesium alkoxide in an alcohol with a solution containing a source of lithium in an alcohol, to obtain a ratio of magnesium metal to lithium metal; hydrolyzing the magnesium alkoxide in the solution to form a gel; and calcining the gel to form a catalyst which is effective for converting methane to ethane and ethylene.

Experimental research on ball lightning

International Nuclear Information System (INIS)

Ofuruton, H.; Ohtsuki, Y.H.

1990-01-01

Experiments on producing ball lightning were made with discharge in flammable gas and/or aerosol. A long lifetime (2 s) ball lightning was observed in 2.7 % ethane and 100 cm 3 cotton fibers, and in 1.5 % methane and 1.9 % ethane

Influence of mo-doping on VPO catalyst for partial oxidation of Ethane

International Nuclear Information System (INIS)

Fakeeha, A. H.; Soliman, M. A.; Alwahabi, S. M; Fahmy, Y. M; Ibrahim, A. A.

2005-01-01

Six MoVPO catalysts were prepared with Mo/V ratios of 0.0, 0.05, 0.1, 0.2, 0.3, 0.5 and P/V of 1.15 for all catalyst, using an isobutanol-benzylacohol solvent. Molydenum was introduced to the VPO catalyst by impregnation. XRD, ICP, BET and SEM were used for the catalyst characterization. A maximum acetic acid yield of 1.1% was obtained using contact time of 3.6 sec. at 573 K and 1360 kPa using VPO catalyst with Mo/V ratio of 0.2 calcined at 723 K under nitrogen flow. At these conditions the ethane conversion was 2.8% and acetic acid and ethylene selectivities were about equal at 37%. Mo has the effect of decreasing the ethane conversion and increasing acetic acid selectively with the initial increase of Mo/V ratio then the selectivity drop to zero at Mo/V ratio then the selectivity drop to zero at Mo/V=o.5. It was found that exposing the catalyst to a reactant mixture lean in ethane at elevated temperature overnight before starting the reaction resulted in an increase in acetic acid selectivity. (author)

Estimation of incremental reactivities for multiple day scenarios: an application to ethane and dimethyoxymethane

Science.gov (United States)

Stockwell, William R.; Geiger, Harald; Becker, Karl H.

Single-day scenarios are used to calculate incremental reactivities by definition (Carter, J. Air Waste Management Assoc. 44 (1994) 881-899.) but even unreactive organic compounds may have a non-negligible effect on ozone concentrations if multiple-day scenarios are considered. The concentration of unreactive compounds and their products may build up over a multiple-day period and the oxidation products may be highly reactive or highly unreactive affecting the overall incremental reactivity of the organic compound. We have developed a method for calculating incremental reactivities for multiple days based on a standard scenario for polluted European conditions. This method was used to estimate maximum incremental reactivities (MIR) and maximum ozone incremental reactivities (MOIR) for ethane and dimethyoxymethane for scenarios ranging from 1 to 6 days. It was found that the incremental reactivities increased as the length of the simulation period increased. The MIR of ethane increased faster than the value for dimethyoxymethane as the scenarios became longer. The MOIRs of ethane and dimethyoxymethane increased but the change was more modest for scenarios longer than 3 days. MOIRs of both volatile organic compounds were equal within the uncertainties of their chemical mechanisms by the 5 day scenario. These results show that dimethyoxymethane has an ozone forming potential on a per mass basis that is only somewhat greater than ethane if multiple-day scenarios are considered.

Thermal Tuning of Ethylene/Ethane Selective Cavities of Intrinsically Microporous Polymers

KAUST Repository

Salinas, Octavio

2016-06-21

Ethylene is the most important organic molecule with regard to production volume. Therefore, the energy spent in its separation processes, based on old-fashioned distillation, takes approx. 33% of total operating costs. Membranes do not require significant thermal energy input; therefore, membrane processes may separate hydrocarbons cheaply and just as reliably as distillation columns. Olefin/paraffin separations are the future targets of commercial membrane applications, provided high-performing materials become available at reasonable prices. This thesis addresses the development of advanced carbon molecular sieve (CMS) membranes derived from intrinsically microporous polymers (PIMs). Chronologically, Chapter 4 of this work reports the evaluation of PIMs as potential ethylene/ethane selective materials, while Chapters 5 to 7 propose PIMs as carbonization precursors. The gravimetric sorption studies conducted in this work regarding both the polymers and their heated-derivatives revealed that this separation is entirely controlled by diffusion differences. The pristine polymers examined in this study presented BET surface areas from 80 to 720 m2g-1. Furthermore, the effect of using bromine-substituted PIM-polyimides elucidated a boost in ethylene permeability, but with a significant drop in selectivity. The hydroxyl functionalization of PIM-polyimides was confirmed as a valuable strategy to increase selectivity. Functionalized PMDA-HSBF is the most selective polyimide of intrinsic microporosity known to date (= 5.1) due to its hydrogen-bonded matrix. In spite of their novelty, pristine PIMs based on the spirobisindane moiety were not tight enough to distinguish between the 0.2 Å difference in diameter of the ethylene/ethane molecules. Therefore, they did not surpass the upper bound limit performance of known polymeric membranes. Nevertheless, the carbons derived from these polymers were excellent ethylene/ethane sieves by virtue of their narrow and tight

Determination of halogens by flame emission of metal halogenides

International Nuclear Information System (INIS)

Henrion, G.; Marquardt, D.; Stoecker, B.

1979-01-01

The A-B systems InF, InCl, InBr, and InI have been excited by laminar H 2 -N 2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10 -4 molar solutions with errors of 2 to 10 per cent. (author)

High-temperature peaks of thermostimulated luminescence in the ammonium halogens

International Nuclear Information System (INIS)

Kim, L.M.; Musenova, Eh.K.; Mukhamedrakhimov, K.U.

2003-01-01

The ammonium halogen crystals (AHC) are the close analogs of the alkali halogen crystals by the type of chemical bonds and crystal lattice structure. The ammonium halogen after irradiation by X-rays within 80-300 K range have two peaks of thermo-stimulation luminescence. Its maximums in dependence of anions type are in the 110-120 K and 170-180 K ranges. The first range is related with activation of auto-localized holes migration, and the second one - with the NH 3 + defects decay. Experimentally is established, that the pure ammonium halogens have memory about the previous irradiation at heating up to 300 K. After repeat irradiation the recombination luminescence high-temperature peak's shoulder is appearing. The second luminescence peak's shoulder revealing does not depend on the impurity center nature. It is known, that in the AHC there is the next thermo-stimulation luminescence peak within 340-360 K. The thermal annealing of this peak leads to the memory effect disappearance. So, the observing phenomenon is related with own defect of the matrix in the cation sublattice. Experimentally is established, that at a room temperature the AHC memorizing about previous irradiation during 20 h

Retention efficiencies of halogenated and non-halogenated hydrocarbons in selected wetland ecosystem in Lake Victoria Basin

Directory of Open Access Journals (Sweden)

Shadrack Mule

2015-06-01

Full Text Available The determination of retention efficiencies of halogenated and non-halogenated hydrocarbon in selected wetland ecosystems in Lake Victoria basin was carried out. Qualitative and quantitative determination of the presence of residual hydrocarbons in Kigwal/Kimondi, Nyando and Nzoia wetland ecosystems using Gas Chromatography - Mass Spectrometer (GC-MS instrument indicated the presence of residual organochlorines, organophosphorus, carbamates and synthetic pyrethroid hydrocarbons in water, sediment and plant materials. In order to compare the retention efficiencies of the wetlands, the wetland ecosystems were divided into three different sections, namely: inlet, mid and outlet. Calculations of mass balances of residual halogenated and non-halogenated hydrocarbons at the respective sections was done taking into account the partition of the studied compounds in samples of water, sediments and papyrus reed plant materials and analyzed using validated Gas Chromatography - Mass Spectrometer (GC-MS method. From the analysis, several residual hydrocarbons namely: bendiocarb, benzene hexachloride (BHC, carbaryl, cypermethrin, decis, deltamethrin, diazinon, dieldrin, DDT, DDD, DDE, malathion, propoxur, sumithion, 5-phenylrhodanine, 1,3,5-trichlorobenzene, 1-(2-phenoxybenzylhydrazine were detected and quantified. The levels of the selected residual hydrocarbons in water samples were used to calculate the retention efficiencies of a specific hydrocarbon and the values recorded. Generally, River Nyando wetland recorded mean percentage retention efficiencies of 76 and 94% for dry and rainy seasons respectively; Kigwal/Kimondi wetland had seasonal mean percentage retention efficiencies of 63 to 78%. River Nzoia also had calculated seasonal mean percentage retention efficiencies of between 56 to 88%. Dry season had lower mean percentages retention efficiencies as compared to rainy season in the three wetlands of interest during the period of study. The study

Alternative routes for the chemical industry regarding US shale gas

Energy Technology Data Exchange (ETDEWEB)

Kneissel, B. [Stratley AG, Koeln (Germany)

2013-11-01

Cracking ethane from wet shale gas in North America sets a bench mark to global ethylene production costs. Regarding very attractive ethane prices from extraction of low cost wet shale gas we suggest in North America ethylene production costs will roughly vary between 400 and 600 $/ t. As in other parts of the world, except Middle East, the availability of ethane seems to be more limited other sources for ethylene, such as methane, coal and biomass are investigated. Oxidative coupling of methane (OCM) has its limits and may only lead to competitive production costs for large scale operations. Coal converted to ethylene via calcium carbide and subsequent hydrogenation may hardly be a viable answer. Ethylene derived by dehydration of ethanol from fermentation of corn sugar may be an answer for very low crop prices. Further research on the conversion of methane with emphasis on its industrial implementation as a major carbon resource is recommended. (orig.)

Titan's Carbon Isotopic Ratio: A Clue To Atmospheric Evolution?

Science.gov (United States)

Nixon, C. A.; Jennings, D. E.; Romani, P. N.; Jolly, A.; Teanby, N. A.; Irwin, P. G.; Bézard, B.; Vinatier, S.; Coustenis, A.; Flasar, F. M.

2009-12-01

In this presentation we describe the latest results to come from Cassini CIRS and ground-based telescopic measurements of Titan's 12C/13C ratio in atmospheric molecules, focusing on hydrocarbons. Previously, the Huygens GCMS instrument measured 12CH4/13CH4 to be 82±1 (Niemann et al., Nature, 438, 779-784, 2005), substantially and significantly lower than the VPDB inorganic Earth standard of 89.4. It is also at odds with measurements for the giant planets. Cassini CIRS infrared spectra have confirmed this enhancement in 13CH4, but also revealed that the ratio in ethane, the major photochemical product of methane photolysis, does not appear enhanced (90±7) (Nixon et al.. Icarus, 195, 778-791, 2008) and is compatible with the terrestrial and combined giant planet value (88±7, Sada et al., Ap. J., 472, p. 903-907, 1996). Recently-published results from spectroscopy using the McMath-Pierce telescope at Kitt Pitt (Jennings et al., JCP, 2009, in press) have confirmed this deviation between methane and ethane, and an explanation has been proposed. This invokes a kinetic isotope effect (KIE) in the abstraction of methane by ethynyl, a major ethane formation pathway, to preferentially partition 12C into ethane and leave an enhancement in atmospheric 13CH4 relative to the incoming flux from the reservoir. Modeling shows that a steady-state solution exists where the 12C/13C methane is decreased from the reservoir value by exactly the KIE factor (the ratio of 12CH4 to 13CH4 abstraction reaction rates): which is plausibly around 1.08, very close to the observed amount. However, a second solution exists in which we are observing Titan about ~1 methane lifetime after a major injection of methane into the atmosphere which is rapidly being eliminated. Updated measurements by Cassini CIRS of both the methane and ethane 12C/13C ratios will be presented, along with progress in interpreting this ratio. In addition, we summarize the 12C/13C measurements by CIRS in multiple other Titan

OPTICAL CONSTANTS AND BAND STRENGTHS OF CH4:C2H6 ICES IN THE NEAR- AND MID-INFRARED

International Nuclear Information System (INIS)

Molpeceres, Germán; Ortigoso, Juan; Escribano, Rafael; Maté, Belén; Satorre, Miguel Angel; Millán, Carlos

2016-01-01

We present a spectroscopic study of methane–ethane ice mixtures. We have grown CH 4 :C 2 H 6 mixtures with ratios 3:1, 1:1, and 1:3 at 18 and 30 K, plus pure methane and ethane ices, and have studied them in the near-infrared (NIR) and mid-infrared (MIR) ranges. We have determined densities of all species mentioned above. For amorphous ethane grown at 18 and 30 K we have obtained a density of 0.41 and 0.54 g cm −3 , respectively, lower than a previous measurement of the density of the crystalline species, 0.719 g cm −3 . As far as we know this is the first determination of the density of amorphous ethane ice. We have measured band shifts of the main NIR methane and ethane features in the mixtures with respect to the corresponding values in the pure ices. We have estimated band strengths of these bands in the NIR and MIR ranges. In general, intensity decay in methane modes was detected in the mixtures, whereas for ethane no clear tendency was observed. Optical constants of the mixtures at 30 and 18 K have also been evaluated. These values can be used to trace the presence of these species in the surface of trans-Neptunian objects. Furthermore, we have carried out a theoretical calculation of these ice mixtures. Simulation cells for the amorphous solids have been constructed using a Metropolis Monte Carlo procedure. Relaxation of the cells and prediction of infrared spectra have been carried out at density functional theory level.

Crystal structures of three co-crystals of 1,2-bis-(pyridin-4-yl)ethane with 4-alk-oxy-benzoic acids: 4-eth-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1), 4-n-propoxybenzoic acid-1,2-bis(pyridin-4-yl)ethane (2/1) and 4-n-but-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1).

Science.gov (United States)

Tabuchi, Yohei; Gotoh, Kazuma; Ishida, Hiroyuki

2015-11-01

The crystal structures of three hydrogen-bonded co-crystals of 4-alk-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1), namely, 2C9H10O3·C12H12N2, (I), 2C10H12O3·C12H12N2, (II), and 2C11H14O3·C12H12N2, (III), have been determined at 93, 290 and 93 K, respectively. In (I), the asymmetric unit consists of one 4-eth-oxy-benzoic acid mol-ecule and one half-mol-ecule of 1,2-bis-(pyridin-4-yl)ethane, which lies on an inversion centre. In (II) and (III), the asymmetric units each comprise two crystallographically independent 4-alk-oxy-benzoic acid mol-ecules and one 1,2-bis-(pyridin-4-yl)ethane mol-ecule. In each crystal, the two components are linked by O-H⋯N hydrogen bonds, forming a linear hydrogen-bonded 2:1unit of the acid and the base. Similar to the structure of 2:1 unit of (I), the units of (II) and (III) adopt nearly pseudo-inversion symmetry. The 2:1 units of (I), (II) and (III) are linked via C-H⋯O hydrogen bonds, forming tape structures.

Pressure and temperature dependencies of o-Ps annihilation rates in ethane

International Nuclear Information System (INIS)

Sharma, S.C.; Juengerman, E.M.

1985-01-01

The authors report new results on the behavior of the sharp enhancement seen recently in the pickoff annihilation rates of orthopositronium atoms as functions of pressure and temperature of ethane gas

An Overview of Recent Advances of the Catalytic Selective Oxidation of Ethane to Oxygenates

Directory of Open Access Journals (Sweden)

Robert D. Armstrong

2016-05-01

Full Text Available The selective partial oxidation of short chain alkanes is a key challenge within catalysis research. Direct ethane oxidation to oxygenates is a difficult aim, but potentially rewarding, and it could lead to a paradigm shift in the supply chain of several bulk chemicals. Unfortunately, low C–H bond reactivity and kinetically labile products are just some reasons affecting the development and commercialisation of such processes. Research into direct ethane oxidation is therefore disparate, with approaches ranging from oxidation in the gas phase at high temperatures to enzyme catalysed hydroxylation under ambient conditions. Furthermore, in overcoming the barrier posed by the chemically inert C–H bond a range of oxidants have been utilised. Despite years of research, this remains an intriguing topic from both academic and commercial perspectives. Herein we describe some recent developments within the field of catalytic ethane oxidation focusing on the formation of oxygenated products, whilst addressing the key challenges which are still to be overcome.

Aminopropyl-functionalized ethane-bridged periodic mesoporous organosilica spheres: preparation and application in liquid chromatography.

Science.gov (United States)

Li, Chun; Di, Bin; Hao, Weiqiang; Yan, Fang; Su, Mengxiang

2011-01-21

A synthetic approach for synthesizing spherical aminopropyl-functionalized ethane-bridged periodic mesoporous organosilicas (APEPMOs) is reported. The mesoporous material was prepared by a one-step co-condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) and 3-aminopropyltriethoxysilane (APTES) using cetyltrimethylammonium chlorine (C(18)TACl) as a template with the aid of a co-solvent (methanol) in basic medium. The APEPMOs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. It was shown that this material exhibited spherical morphology, ordered cubic mesostructure and good mechanical strength. The APEPMOs were tested as a potential stationary phase for liquid chromatography (LC) because the column exhibited reduced back pressure. Moreover, they exhibited good chemical stability in basic mobile phase, which can be ascribed to the ethane groups in the mesoporous framework. Copyright © 2010 Elsevier B.V. All rights reserved.

Halogens determination in vegetable NBS standard reference materials

International Nuclear Information System (INIS)

Stella, R.; Genova, N.; Di Casa, M.

1977-01-01

Levels of all four halogens in Orchard Leaves, Pine Needles and Tomato Leaves NBS reference standards were determined. For fluorine a spiking isotope dilution method was used followed by HF absorption on glass beads. Instrumental nuclear activation analysis was adopted for chlorine and bromine determination. Radiochemical separation by a distillation procedure was necessary for iodine nuclear activation analysis after irradiation. Activation parameters of Cl, Br and I are reported. Results of five determinations for each halogen in Orchard Leaves, Pine Needles and Tomato Leaves NBS Standard Materials and Standard deviations of the mean are reported. (T.I.)

Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

Directory of Open Access Journals (Sweden)

Janet E. Del Bene

2017-11-01

Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

Science.gov (United States)

Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

1998-01-01

Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

Historical trends and ecological risks of polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs) in a mangrove in South China.

Science.gov (United States)

Wu, Qihang; Liu, Xucheng; Liang, Chaozong; Leung, Jonathan Y S; Li, Huosheng; Chen, Shejun; Mai, Bixian; Miao, Shenyu; Chen, Yongheng; Wu, Zhifeng; Chen, Zhanghe

2017-12-01

While the production of polybrominated diphenyl ethers (PBDEs) was gradually phased out in the last decade, they may still pose hidden danger to the environment due to their toxicity and persistence. On the other hand, alternative halogenated flame retardants (AHFRs) have been increasingly used as substitutes for PBDEs and may further worsen environmental health. To determine the environmental impact of PBDEs and AHFRs, we examined the historical trends and ecological risks of PBDEs and AHFRs in a typical industrialized city in South China by measuring their concentrations in mangrove sediment. Results showed that the concentrations of PBDEs increased abruptly from 1997 to 2009 due to the use of commercial deca-BDE mixture, but were stabilized in recent years. The concentrations of AHFRs, mainly contributed by decabromodiphenyl ethane (DBDPE), kept increasing from 1997 onwards. Based on the temporal trends, DBDPE is predicted to be predominant over BDE 209 in future. Despite the observed similar concentration between BDE 209 and DBDPE, the former posed a high ecological risk, while the ecological risk of the latter was negligible. Therefore, more attention is required to manage the contamination of BDE 209 in the environment. Copyright © 2017 Elsevier B.V. All rights reserved.

Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

Science.gov (United States)

Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

2018-03-01

The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

Halogen degassing during ascent and eruption of water-poor basaltic magma

Science.gov (United States)

Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

2009-01-01

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Is Optical Gas Imaging Effective for Detecting Fugitive Methane Emissions? - A Technological and Policy Perspective

Science.gov (United States)

Ravikumar, A. P.; Wang, J.; Brandt, A. R.

2016-12-01

Mitigating fugitive methane emissions from the oil and gas industry has become an important concern for both businesses and regulators. While recent studies have improved our understanding of emissions from all sectors of the natural gas supply chain, cost-effectively identifying leaks over expansive natural gas infrastructure remains a significant challenge. Recently, the Environmental Protection Agency (EPA) has recommended the use of optical gas imaging (OGI) technologies to be used in industry-wide leak detection and repair (LDAR) programs. However, there has been little to no systematic study of the effectiveness of infrared-camera-based OGI technology for leak detection applications. Here, we develop a physics-based model that simulates a passive infrared camera imaging a methane leak against varying background and ambient conditions. We verify the simulation tool through a series of large-volume controlled release field experiments wherein known quantities of methane were released and imaged from a range of distances. After simulator verification, we analyze the effects of environmental conditions like temperature, wind, and imaging background on the amount of methane detected from a statistically representative survey program. We also examine the effects of LDAR design parameters like imaging distance, leak size distribution, and gas composition. We show that imaging distance strongly affects leak detection - EPA's expectation of a 60% reduction in fugitive emissions based on a semi-annual LDAR survey will be realized only if leaks are imaged at a distance less than 10 m from the source under ideal environmental conditions. Local wind speed is also shown to be important. We show that minimum detection limits are 3 to 4 times higher for wet-gas compositions that contain a significant fraction of ethane and propane, resulting a significantly large leakage rate. We also explore the importance of `super-emitters' on the performance of an OGI-based leak

Enhancing aerobic biodegradation of 1,2-dibromoethane in groundwater using ethane or propane and inorganic nutrients.

Science.gov (United States)

Hatzinger, Paul B; Streger, Sheryl H; Begley, James F

2015-01-01

1,2-Dibromoethane (ethylene dibromide; EDB) is a probable human carcinogen that was previously used as both a soil fumigant and a scavenger in leaded gasoline. EDB has been observed to persist in soils and groundwater, particularly under oxic conditions. The objective of this study was to evaluate options to enhance the aerobic degradation of EDB in groundwater, with a particular focus on possible in situ remediation strategies. Propane gas and ethane gas were observed to significantly stimulate the biodegradation of EDB in microcosms constructed with aquifer solids and groundwater from the FS-12 EDB plume at Joint Base Cape Cod (Cape Cod, MA), but only after inorganic nutrients were added. Ethene gas was also effective, but rates were appreciably slower than for ethane and propane. EDB was reduced to ethane gas and inorganic nutrients. An enrichment culture (BE-3R) that grew on ethane or propane gas but not EDB was obtained from the site materials. The degradation of EDB by this culture was inhibited by acetylene gas, suggesting that degradation is catalyzed by a monooxygenase enzyme. The BE-3R culture was also observed to biodegrade 1,2-dichloroethane (DCA), a compound commonly used in conjunction with EDB as a lead scavenger in gasoline. The data suggest that addition of ethane or propane gas with inorganic nutrients may be a viable option to enhance degradation of EDB in groundwater aquifers to below current state or federal MCL values. Copyright © 2014 Elsevier B.V. All rights reserved.

Simulation and Characterization of Methane Hydrate Formation

Science.gov (United States)

Dhakal, S.; Gupta, I.

2017-12-01

The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate

Density dependence of stopping cross sections measured in liquid ethane

International Nuclear Information System (INIS)

Both, G.; Krotz, R.; Lohmer, K.; Neuwirth, W.

1983-01-01

Electronic stopping cross sections for 7 Li projectiles (840--175 keV) have been measured with the inverted Doppler-shift attenuation method in liquid ethane (C 2 H 6 ) at two different densities. The density of the target has been varied by changing the temperature, and measurements have been performed at 0.525 g/cm 3 (199 K) and 0.362 g/cm 3 (287 K). At the higher density the stopping cross section is about 2% smaller. This result agrees with a calculation of the stopping cross section of liquid ethane, applying Lindhard's theory in the local-density approximation using a simple model of the liquid. It is also in agreement with various observations of the so-called physical-state effect, which show that the stopping cross section of the same substance is smaller in a condensed phase than in the gaseous one

Kinetics of physical adsorption of ethane on Ir(110)-(1×2): Molecular beam reflectivity measurements and Monte Carlo simulations

OpenAIRE

Kang, H. C.; Mullins, C. B.; Weinberg, W. H.

1990-01-01

Experimental results, obtained using a reflectivity method, for the probability of physical adsorption of ethane on the Ir(110)-(1×2) surface are presented. We analyze these results using Monte Carlo simulations and show that physical adsorption can occur either directly or through a precursor state in which an ethane molecule is trapped in a second layer above a first layer of physically adsorbed ethane. From the Monte Carlo simulations, we are able to establish that the energy barrier for d...

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

Science.gov (United States)

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

Risk assessment for halogenated solvents

International Nuclear Information System (INIS)

Travis, C.C.

1988-01-01

A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

Development of halogen-free cables for nuclear power plants

International Nuclear Information System (INIS)

Yamamoto, Mitsuo; Ito, Kazumi; Yaji, Takeo; Yoshida, Shin; Sakurai, Takako; Matsushita, Shigetoshi.

1990-01-01

On the occasion where serious fire accidents were experienced in the past, the need for making flame-retardant wire and cable incombustible took place and has since been generalizing. Various sorts of flame-retardant cables have already been developed and been actually used. From the viewpoint of avoiding the interference with the evacuation and fire-fighting activity in case of fire or the secondary accidents such as corrosion of the distributing panel, etc., the demand for non-halogen flame-retardant cable has rapidly been increasing in recent years in some fields of general industries, because this specific cable would generate the least amount of toxic smoke or corrosive gas even when it should burn. Similar demand has been increasing also for the cable used for nuclear power plants. In this field, earnest desire has been made for the development of non-halogen flame-retardant cable having specific environmental resistance specially required at nuclear power plants in addition to the properties and capacities required in general industries. The authors have continued examinations on the anti-environmental properties of the materials for cable such as long heat resistance, radiation resistance, steam resistance and succeeded in completing various sorts of non-halogen flame-retardant cable for nuclear power plants. In this report, we will introduce various features of the cable we have developed this time as well as the long-term reliability of non-halogen flame-retardant materials. (author)

Characteristics of atmospheric non-methane hydrocarbons during high PM 10 episodes and normal days in Foshan, China

Science.gov (United States)

Guo, Songjun; Tan, Jihua; Ma, Yongliang; Yang, Fumo; Yu, Yongchan; Wang, Jiewen

2011-08-01

Atmospheric non-methane hydrocarbons (NMHCs) were firstly studied during high PM 10 episodes and normal days in December 2008 in Foshan, China. Ethyne, ethene, i-pentane, toluene, ethane and propane are six abundant hydrocarbons, accounting for round 80% of total NMHCs. Both diurnal variations and concentration ratios of morning (evening)/afternoon implied vehicular emission for most hydrocarbons. Correlation coefficients (R 2) of ethene, propene, i-butene, benzene, toluene and i-/n-butanes with ethyne were 0.60-0.88 (they were 0.64-0.88 during high PM 10 episode and 0.60-0.85 in normal days) except for ethene and i-butene in normal days, indicating these hydrocarbons are mainly related to vehicular emission. It suggests liquefied petroleum gas (LPG) and natural gas (NG) leakages are responsible for propane and ethane, respectively. The measured mean benzene/toluene (B/T) ratio (wt/wt) was 0.45 ± 0.29 during total sampling periods together with R 2 analysis, again indicating vehicular emission is main contributor to ambient hydrocarbons. And the lower B/T ratio (0.29 ± 0.11) during high PM 10 episodes than that (0.75 ± 0.29) in normal days is likely caused by air transport containing low B/T value (0.23) from Guangzhou as well as solvent application containing toluene in Foshan.

Modeling the methane hydrate formation in an aqueous film submitted to steady cooling

Energy Technology Data Exchange (ETDEWEB)

Avendano-Gomez, J.R. [ESIQIE, Laboratorio de Ingenieria Quimica Ambiental, Mexico (Mexico). Inst. Politecnico Nacional; Garcia-Sanchez, F. [Laboratorio de Termodinamica, Mexico (Mexico). Inst. Mexicano del Petroleo; Gurrola, D.V. [UPIBI, Laboratorio de Diseno de Plantas, Mexico (Mexico). Inst. Politecnico Nacional

2008-07-01

Gas hydrates, or clathrate hydrates, are ice-like compounds that results from the kinetic process of crystallization of an aqueous solution supersaturated with a dissolved gas. This paper presented a model that took into account two factors involved in the hydrate crystallization, notably the stochastic nature of crystallization that causes sub-cooling and the heat resulting from the exothermic enthalpy of hydrate formation. The purpose of this study was to model the thermal evolution inside a hydrate forming system which was submitted to an imposed steady cooling. The study system was a cylindrical thin film of aqueous solution at 19 Mpa. The study involved using methane as the hydrate forming molecule. It was assumed that methane was homogeneously dissolved in the aqueous phase. Ethane hydrate was formed through a kinetic process of nucleation and crystallization. In order to predict the onset time of nucleation, the induction time needed to be considered. This paper discussed the probability of nucleation as well as the estimation of the rate of nucleation. It also presented the mathematical model and boundary conditions. These included assumptions and derivation of the model; boundary conditions; initial conditions; and numerical solution of the model equation. It was concluded that the heat source must be considered when investigating crystallization effects. 34 refs., 2 tabs., 2 figs.

The rotational barrier in ethane: a molecular orbital study.

Science.gov (United States)

Quijano-Quiñones, Ramiro F; Quesadas-Rojas, Mariana; Cuevas, Gabriel; Mena-Rejón, Gonzalo J

2012-04-20

The energy change on each Occupied Molecular Orbital as a function of rotation about the C-C bond in ethane was studied using the B3LYP, mPWB95 functional and MP2 methods with different basis sets. Also, the effect of the ZPE on rotational barrier was analyzed. We have found that σ and π energies contribution stabilize a staggered conformation. The σ(s) molecular orbital stabilizes the staggered conformation while the stabilizes the eclipsed conformation and destabilize the staggered conformation. The π(z) and molecular orbitals stabilize both the eclipsed and staggered conformations, which are destabilized by the π(v) and molecular orbitals. The results show that the method of calculation has the effect of changing the behavior of the energy change in each Occupied Molecular Orbital energy as a function of the angle of rotation about the C-C bond in ethane. Finally, we found that if the molecular orbital energy contribution is deleted from the rotational energy, an inversion in conformational preference occurs.

The Rotational Barrier in Ethane: A Molecular Orbital Study

Directory of Open Access Journals (Sweden)

Gonzalo J. Mena-Rejón

2012-04-01

Full Text Available The energy change on each Occupied Molecular Orbital as a function of rotation about the C-C bond in ethane was studied using the B3LYP, mPWB95 functional and MP2 methods with different basis sets. Also, the effect of the ZPE on rotational barrier was analyzed. We have found that σ and π energies contribution stabilize a staggered conformation. The σ_s molecular orbital stabilizes the staggered conformation while the  stabilizes the eclipsed conformation and destabilize the staggered conformation. The π_z and  molecular orbitals stabilize both the eclipsed and staggered conformations, which are destabilized by the π_v and  molecular orbitals. The results show that the method of calculation has the effect of changing the behavior of the energy change in each Occupied Molecular Orbital energy as a function of the angle of rotation about the C–C bond in ethane. Finally, we found that if the molecular orbital energy contribution is deleted from the rotational energy, an inversion in conformational preference occurs.

FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

Energy Technology Data Exchange (ETDEWEB)

John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

2003-07-01

Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

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diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA ... corresponding amines with alkyl halide to bear diammines of the same class with different substituents. ... Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2-diyldiimino)diacetic acid. Bull. Chem. Soc. Ethiop.

Dose and temperature criteria for radiation chlorination of ethane

International Nuclear Information System (INIS)

Prasil, Z.

1979-01-01

General criteria determining the region of dose rates and temperatures at which a radiation-induced chain reaction proceeds are applied to a series of subsequent and competitive chain reactions of the chlorination of ethane and its derivatives. The calculations presume that the reactions proceed in an ideal through-flow chemical reactor with a piston flow. (M.S.)

Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

Science.gov (United States)

Sumner, A. J.; Plata, D.

2017-12-01

Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

The second virial coefficients of some halogenated ethanes

Science.gov (United States)

Kohler, Friedrich; van Nhu, Nguyen

The second virial coefficients of 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane and 1-chloro-1,1-difluoroethane have been calculated on the basis of two-centre-Lennard-Jones + superimposed dipole model potentials and compared with experimental results. These can be explained taking into account the reduced dipole moments and the angle between dipole moment and molecular axis.

Size-selective separation of polydisperse gold nanoparticles in supercritical ethane.

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Williams, Dylan P; Satherley, John

2009-04-09

The aim of this study was to use supercritical ethane to selectively disperse alkanethiol-stabilized gold nanoparticles of one size from a polydisperse sample in order to recover a monodisperse fraction of the nanoparticles. A disperse sample of metal nanoparticles with diameters in the range of 1-5 nm was prepared using established techniques then further purified by Soxhlet extraction. The purified sample was subjected to supercritical ethane at a temperature of 318 K in the pressure range 50-276 bar. Particles were characterized by UV-vis absorption spectroscopy, TEM, and MALDI-TOF mass spectroscopy. The results show that with increasing pressure the dispersibility of the nanoparticles increases, this effect is most pronounced for smaller nanoparticles. At the highest pressure investigated a sample of the particles was effectively stripped of all the smaller particles leaving a monodisperse sample. The relationship between dispersibility and supercritical fluid density for two different size samples of alkanethiol-stabilized gold nanoparticles was considered using the Chrastil chemical equilibrium model.

Microfluidic Separation of Ethylene and Ethane Using Frustrated Lewis Pairs.

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Voicu, Dan; Stephan, Douglas W; Kumacheva, Eugenia

2015-12-21

Separation of gaseous olefins and paraffins is one of the most important separation processes in the industry. Development of new cost-effective technologies aims at reducing the high energy consumption during the separation process. Here, we took advantage of the reaction of frustrated Lewis pairs (FLPs) with ethylene to achieve reactive extraction of ethylene from ethylene-ethane mixtures. The extraction was studied using a microfluidic platform, which enabled a rapid, high-throughput assessment of reaction conditions to optimize gas separation efficiency. A separation factor of 7.3 was achieved for ethylene from a 1:1 volume ratio mixture of ethylene and ethane, which corresponded to an extracted ethylene purity of 88 %. The results obtained in the microfluidic studies were validated using infrared spectroscopy. This work paves the way for further development of the FLPs and optimization of reaction conditions, thereby maximizing the separation efficiency of olefins from their mixtures with paraffins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory spectra of C-13 ethane

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Kurtz, Joe; Reuter, Dennis C.; Jennings, Donald E.; Hillman, John J.

1991-01-01

The laboratory infrared spectrum of C-13 monosubstituted ethane has been obtained at high resolution (0.0025/cm) using the McMath Fourier transform spectrometer at Kitt Peak National Observatory in May 1990. A preliminary analysis of the nu12 rQ0 branch (substituted species) suggests that its intensity is 1.15 + or - 0.05 times stronger than the equivalent nu9 branch in the normal (C-12)2H6 species. This result leads to a correction of a previously published estimate for the C-12/C-13 ratio in the atmosphere of Jupiter from about 94 to about 106.

Investigating Multiphase Flow Phenomena in Fine-Grained Reservoir Rocks: Insights from Using Ethane Permeability Measurements over a Range of Pore Pressures

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Eric Aidan Letham

2018-01-01

Full Text Available The ability to quantify effective permeability at the various fluid saturations and stress states experienced during production from shale oil and shale gas reservoirs is required for efficient exploitation of the resources, but to date experimental challenges prevent measurement of the effective permeability of these materials over a range of fluid saturations. To work towards overcoming these challenges, we measured effective permeability of a suite of gas shales to gaseous ethane over a range of pore pressures up to the saturated vapour pressure. Liquid/semiliquid ethane saturation increases due to adsorption and capillary condensation with increasing pore pressure resulting in decreasing effective permeability to ethane gas. By how much effective permeability to ethane gas decreases with adsorption and capillary condensation depends on the pore size distribution of each sample and the stress state that effective permeability is measured at. Effective permeability decreases more at higher stress states because the pores are smaller at higher stress states. The largest effective permeability drops occur in samples with dominant pore sizes in the mesopore range. These pores are completely blocked due to capillary condensation at pore pressures near the saturated vapour pressure of ethane. Blockage of these pores cuts off the main fluid flow pathways in the rock, thereby drastically decreasing effective permeability to ethane gas.

In vitro dermal absorption of decabromodiphenyl ethane in rat and human skin

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U.S. Environmental Protection Agency — In vitro dermal absorption of decabromodiphenyl ethane in rat and human skin. This dataset is associated with the following publication: Knudsen, G., J.M. Sanders,...

Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2 ...

African Journals Online (AJOL)

ethane-1,2-diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA were characterized by physical measurements including elemental analysis, IR, UV-Visible, magnetic susceptibilities and ...

MethaneSat: Detecting Methane Emissions in the Barnett Shale Region

Science.gov (United States)

Propp, A. M.; Benmergui, J. S.; Turner, A. J.; Wofsy, S. C.

2017-12-01

In this study, we investigate the new information that will be provided by MethaneSat, a proposed satellite that will measure the total column dry-air mole fraction of methane at 1x1 km or 2x2 km spatial resolution with 0.1-0.2% random error. We run an atmospheric model to simulate MethaneSat's ability to characterize methane emissions from the Barnett Shale, a natural gas province in Texas. For comparison, we perform observation system simulation experiments (OSSEs) for MethaneSat, the National Oceanic and Atmospheric administration (NOAA) surface and aircraft network, and Greenhouse Gases Observing Satellite (GOSAT). The results demonstrate the added benefit that MethaneSat would provide in our efforts to monitor and report methane emissions. We find that MethaneSat successfully quantifies total methane emissions in the region, as well as their spatial distribution and steep gradients. Under the same test conditions, both the NOAA network and GOSAT fail to capture this information. Furthermore, we find that the results for MethaneSat depend far less on the prior emission estimate than do those for the other observing systems, demonstrating the benefit of high sampling density. The results suggest that MethaneSat would be an incredibly useful tool for obtaining detailed methane emission information from oil and gas provinces around the world.

Ambient air/near-field measurements of methane and Volatile Organic Compounds (VOCs) from a natural gas facility in Northern Europe

Science.gov (United States)

Baudic, Alexia; Gros, Valérie; Bonsang, Bernard; Baisnee, Dominique; Vogel, Félix; Yver Kwok, Camille; Ars, Sébastien; Finlayson, Andrew; Innocenti, Fabrizio; Robinson, Rod

2015-04-01

Since the 1970's, the natural gas consumption saw a rapid growth in large urban centers, thus becoming an important energy resource to meet continuous needs of factories and inhabitants. Nevertheless, it can be a substantial source of methane (CH4) and pollutants in urban areas. For instance, we have determined that about 20% of Volatile Organic Compounds (VOCs) in downtown Paris are originating from this emission source (Baudic, Gros et al., in preparation). Within the framework of the "Fugitive Methane Emissions" (FuME) project (Climate-KIC, EIT); 2-weeks gas measurements were conducted at a gas compressor station in Northern Europe. Continuous ambient air measurements of methane and VOCs concentrations were performed using a cavity ring-down spectrometer (model G2201, Picarro Inc., Santa Clara, USA) and two portable GC-FID (Chromatotec, Saint-Antoine, France), respectively. On-site near-field samplings were also carried out at the source of two pipelines using stainless steel flasks (later analyzed with a laboratory GC-FID). The objective of this study aims to use VOCs as additional tracers in order to better characterize the fugitive methane emissions in a complex environment, which can be affected by several urban sources (road-traffic, others industries, etc.). Moreover, these measurements have allowed determining the chemical composition of this specific source. Our results revealed that the variability of methane and some VOCs was (rather) well correlated, especially for alkanes (ethane, propane, etc.). An analysis of selected events with strong concentrations enhancement was performed using ambient air measurements; thus allowing the preliminary identification of different emission sources. In addition, some flasks were also sampled in Paris to determine the local natural gas composition. A comparison between both was then performed. Preliminary results from these experiments will be presented here.

Evaluation of remaining behavior of halogen on the fabrication of MOX pellet containing Am

International Nuclear Information System (INIS)

Ozaki, Yoko; Osaka, Masahiko; Obayashi, Hiroshi; Tanaka, Kenya

2004-11-01

It is important to limit the content of halogen elements, namely fluorine and chlorine that are sources of making cladding material corrode, in nuclear fuel from the viewpoint of quality assurance. The halogen content should be more carefully limited in the MOX fuel containing Americium (Am-MOX), which is fabricated in the Alpha-Gamma Facility (AGF) for irradiation testing to be conducted in the experimental fast reactor JOYO, because fluorine may remain in the sintered pellets owing to a formation of AmF 3 known to have a low vapor pressure and may exceeds the limit of 25 ppm. In this study, a series of experimental determination of halogen element in Am-MOX were performed by a combination method of pyrolysis and ion-chromatography for the purpose of an evaluation of behavior of remaining halogen through the sintering process. Oxygen potential, temperature and time were changed as experimental parameters and their effects on the remaining behavior of halogen were examined. It was confirmed that good pellets, which contained small amount of halogen, could be obtained by the sintering for 3 hour at 1700degC in the oxygen potential range from -520 to -390 kJ/mol. In order to analysis of fluorine chemical form in green pellet, thermal analysis was performed. AmF 3 and PuF 3 have been confirmed to remain in the green pellet. (author)

Development of Halogen-free flame-retardant cable for nuclear power plant

International Nuclear Information System (INIS)

Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

1992-01-01

Conventional flame-retardant cables release a large volume of corrosive and toxic gases as well as smoke while combusted. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and have already been used in telecommunication service, subway and shipboard applications. However, for cables for nuclear power plant, covering materials should also have radiation resistance and other properties, including long-term physical stability. We have developed halogen-free flame-retardant cables for BWR nuclear power plant with sufficient flame retardancy radiation resistance and environmental resistance including steam-exposure resistance all of which are in accordance with Japanese specifications for BWR nuclear cables and have such characteristics as low corrosiveness, low toxicity and low smoke emission. (author)

Development of halogen-free flame-retardant cable for nuclear power plant

International Nuclear Information System (INIS)

Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

1991-01-01

Conventional flame-retardant cables release a large amount of corrosive and toxic gases and also smoke during combustion on fire. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and already used in telecommunication plant, subway and shipboard applications. In the case of nuclear power plant application, cable covering materials should also have radiation resistance and other properties including long-term physical stability. We have developed halogen-free flame-retardant cables for nuclear power plant with sufficient flame retardancy, radiation resistance, and environmental resistance including steam-exposure resistance, all of which are in accordance with Japanese specifications for nuclear cables, and with characteristics as low corrosiveness, low toxicity, and low smoke evolution. (author)

Crystal structure of 1-meth-oxy-2,2,2-tris-(pyrazol-1-yl)ethane.

Science.gov (United States)

Lyubartseva, Ganna; Parkin, Sean; Coleman, Morgan D; Mallik, Uma Prasad

2014-09-01

The title compound, C12H14N6O, consists of three pyrazole rings bound via nitro-gen to the distal ethane carbon of meth-oxy ethane. The dihedral angles between the three pyrazole rings are 67.62 (14), 73.74 (14), and 78.92 (12)°. In the crystal, mol-ecules are linked by bifurcated C-H,H⋯N hydrogen bonds, forming double-stranded chains along [001]. The chains are linked via C-H⋯O hydrogen bonds, forming a three-dimensional framework structure. The crystal was refined as a perfect (0.5:0.5) inversion twin.

Quadrupole type mass spectrometric study of the abstraction reaction between hydrogen atoms and ethane.

Science.gov (United States)

Bayrakçeken, Fuat

2008-02-01

The reactions of photochemically generated deuterium atoms of selected initial translational energy with ethane have been investigated. At each initial energy the relative probability of the atoms undergoing reaction or energy loss on collision with ethane was investigated, and the phenomenological threshold energy was measured as 30+/-5kJmol(-1) for the abstraction from the secondary C-H bonds. The ratio of relative yields per bond, secondary:primary was approximately 3 at the higher energies studied. The correlation of threshold energies with bond dissociation energies, heats of reaction and activation energies is discussed for abstraction reactions with several hydrocarbons.

Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

Energy Technology Data Exchange (ETDEWEB)

Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

2011-07-01

In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error.

Science.gov (United States)

Otero-de-la-Roza, A; Johnson, Erin R; DiLabio, Gino A

2014-12-09

Halogen bonds are formed when a Lewis base interacts with a halogen atom in a different molecule, which acts as an electron acceptor. Due to its charge transfer component, halogen bonding is difficult to model using many common density-functional approximations because they spuriously overstabilize halogen-bonded dimers. It has been suggested that dispersion-corrected density functionals are inadequate to describe halogen bonding. In this work, we show that the exchange-hole dipole moment (XDM) dispersion correction coupled with functionals that minimize delocalization error (for instance, BH&HLYP, but also other half-and-half functionals) accurately model halogen-bonded interactions, with average errors similar to other noncovalent dimers with less charge-transfer effects. The performance of XDM is evaluated for three previously proposed benchmarks (XB18 and XB51 by Kozuch and Martin, and the set proposed by Bauzá et al.) spanning a range of binding energies up to ∼50 kcal/mol. The good performance of BH&HLYP-XDM is comparable to M06-2X, and extends to the "extreme" cases in the Bauzá set. This set contains anionic electron donors where charge transfer occurs even at infinite separation, as well as other charge transfer dimers belonging to the pnictogen and chalcogen bonding classes. We also show that functional delocalization error results in an overly delocalized electron density and exact-exchange hole. We propose intermolecular Bader delocalization indices as an indicator of both the donor-acceptor character of an intermolecular interaction and the delocalization error coming from the underlying functional.

Sources and turnover of organic carbon and methane in fjord and shelf sediments off northern Norway

Science.gov (United States)

Sauer, Simone; Hong, Wei-Li; Knies, Jochen; Lepland, Aivo; Forwick, Matthias; Klug, Martin; Eichinger, Florian; Baranwal, Soma; Crémière, Antoine; Chand, Shyam; Schubert, Carsten J.

2016-10-01

To better understand the present and past carbon cycling and transformation processes in methane-influenced fjord and shelf areas of northern Norway, we compared two sediment cores from the Hola trough and from Ullsfjorden. We investigated (1) the organic matter composition and sedimentological characteristics to study the sources of organic carbon (Corg) and the factors influencing Corg burial, (2) pore water geochemistry to determine the contribution of organoclastic sulfate reduction and methanogenesis to total organic carbon turnover, and (3) the carbon isotopic signature of hydrocarbons to identify the carbon transformation processes and gas sources. High sedimentation and Corg accumulation rates in Ullsfjorden support the notion that fjords are important Corg sinks. The depth of the sulfate-methane-transition (SMT) in the fjord is controlled by the supply of predominantly marine organic matter to the sediment. Organoclastic sulfate reduction accounts for 60% of the total depth-integrated sulfate reduction in the fjord. In spite of the presence of ethane, propane, and butane, we suggest a purely microbial origin of light hydrocarbons in the sediments based on their low δ13C values. In the Hola trough, sedimentation and Corg accumulation rates changed during the deglacial-to-post-glacial transition from approximately 80 cm ka-1 to erosion at present. Thus, Corg burial in this part of the shelf is presently absent. Low organic matter content in the sediment and low rates of organoclastic sulfate reduction (only 3% of total depth-integrated sulfate reduction) entail that the shallow depth of the SMT is controlled mostly by ascending thermogenic methane from deeper sources.

Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

Science.gov (United States)

Miura, Michiko; Wu, Haitao

2013-05-21

The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

Structure-Energy Relationships of Halogen Bonds in Proteins.

Science.gov (United States)

Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

2017-06-06

The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

Ethane-1,1,2-trisphosphonic acid hemihydrate.

Science.gov (United States)

Delain-Bioton, Lise; Lohier, Jean François; Villemin, Didier; Sopková-de Oliveira Santos, Jana; Hix, Gary; Jaffrès, Paul Alain

2008-02-01

Ethane-1,1,2-trisphosphonic acid crystallizes as a hemihydrate, C(2)H(9)O(9)P(3).0.5H(2)O, in which the water O atom lies on an inversion centre in the space group P2(1)/c. The acid component, which contains a short but noncentred O-H...O hydrogen bond, adopts a gauche conformation. The acid components are linked by an extensive series of O-H...O hydrogen bonds to form layers, which are linked into pairs by the water molecules.

Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

KAUST Repository

Ward, Jeremy W.; Li, Ruipeng; Obaid, Abdulmalik; Payne, Marcia M.; Smilgies, Detlef Matthias; Anthony, John Edward; Amassian, Aram; Jurchescu, Oana D.

2014-01-01

new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting

A reconnaissance spatial and temporal assessment of methane and inorganic constituents in groundwater in bedrock aquifers, Pike County, Pennsylvania, 2012-13

Science.gov (United States)

Senior, Lisa A.

2014-01-01

Pike County in northeastern Pennsylvania is underlain by the Devonian-age Marcellus Shale and other shales, formations that have potential for natural gas development. During 2012–13, the U.S. Geological Survey in cooperation with the Pike County Conservation District conducted a reconnaissance study to assess baseline shallow groundwater quality in bedrock aquifers prior to possible shale-gas development in the county. For the spatial component of the assessment, 20 wells were sampled in summer 2012 to provide data on the occurrence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines. For the temporal component of the assessment, 4 of the 20 wells sampled in summer 2012 were sampled monthly from July 2012 through June 2013 to provide data on seasonal variability in groundwater quality. All water samples were analyzed for major ions, nutrients, selected inorganic trace constituents (including metals and other elements), stable isotopes of water, radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and ethene), and, if possible, isotopic composition of methane. Additional analyses for boron and strontium isotopes, age-dating of water, and radium-226 were done on water samples collected from six wells in June 2013.

Phase behaviour in water/hydrocarbon mixtures involved in gas production systems; etude des equilibres des systemes: eau-hydrocarbures-gaz acides dans le cadre de la production de gaz

Energy Technology Data Exchange (ETDEWEB)

Chapoy, A.

2004-11-15

Inside wells, natural gases frequently coexist with water. The gases are in equilibrium with the sub-adjacent aquifer. Many problems are associated with the presence of water during the production, transport and processing of natural gases. Accurate knowledge of the thermodynamic properties of the water/hydrocarbon and water-inhibitor/hydrocarbon equilibria near the hydrate forming conditions, at sub-sea pipeline conditions and during the transport is crucial for the petroleum industry. An apparatus based on a static/analytic method combined with a dilutor apparatus to calibrate on the gas chromatograph (GC) detectors with water was used to measure the water content of binary systems (i.e.: water - methane, ethane - water, nitrogen - water...) as well of a synthetic hydrocarbon gas mixture (i.e.: 94% methane, 4% ethane and 2% n-butane) with and without inhibitor. This same apparatus was also used generate data of methane, ethane, propane, n-butane and nitrogen solubility in water and also the solubilities of a synthetic mixture in water. In-house software has been developed in order to fit and model the experimental data. (author)

Combining tracer flux ratio methodology with low-flying aircraft measurements to estimate dairy farm CH4 emissions

Science.gov (United States)

Daube, C.; Conley, S.; Faloona, I. C.; Yacovitch, T. I.; Roscioli, J. R.; Morris, M.; Curry, J.; Arndt, C.; Herndon, S. C.

2017-12-01

Livestock activity, enteric fermentation of feed and anaerobic digestion of waste, contributes significantly to the methane budget of the United States (EPA, 2016). Studies question the reported magnitude of these methane sources (Miller et. al., 2013), calling for more detailed research of agricultural animals (Hristov, 2014). Tracer flux ratio is an attractive experimental method to bring to this problem because it does not rely on estimates of atmospheric dispersion. Collection of data occurred during one week at two dairy farms in central California (June, 2016). Each farm varied in size, layout, head count, and general operation. The tracer flux ratio method involves releasing ethane on-site with a known flow rate to serve as a tracer gas. Downwind mixed enhancements in ethane (from the tracer) and methane (from the dairy) were measured, and their ratio used to infer the unknown methane emission rate from the farm. An instrumented van drove transects downwind of each farm on public roads while tracer gases were released on-site, employing the tracer flux ratio methodology to assess simultaneous methane and tracer gas plumes. Flying circles around each farm, a small instrumented aircraft made measurements to perform a mass balance evaluation of methane gas. In the course of these two different methane quantification techniques, we were able to validate yet a third method: tracer flux ratio measured via aircraft. Ground-based tracer release rates were applied to the aircraft-observed methane-to-ethane ratios, yielding whole-site methane emission rates. Never before has the tracer flux ratio method been executed with aircraft measurements. Estimates from this new application closely resemble results from the standard ground-based technique to within their respective uncertainties. Incorporating this new dimension to the tracer flux ratio methodology provides additional context for local plume dynamics and validation of both ground and flight-based data.

Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

2015-05-16

This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS and MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.

Geologic Emissions of Methane and C2 - C5 Alkanes at the La Brea Tar Pits, Los Angeles, CA

Science.gov (United States)

Doezema, L. A.; Etiope, G.; Pacheco, C.

2017-12-01

Natural hydrocarbon (oil and gas) seeps are widespread in Los Angeles due to gas migration, along faults, from numerous subsurface petroleum fields. These seeps may represent important natural contributors of methane (CH4) and heavier alkanes (C2-C4) for the atmosphere. Methane flux measurements were made from various locations at the La Brea Tar Pits in Los Angeles, CA. Measurements were made using a closed-chamber method and spectroscopic sensors for CH4 and CO2, at 26 oil-asphalt seeps and 188 other sites, without gas manifestations, homogeneously distributed throughout the park. The molecular C1 - C5 composition of gas released from seeps and soil was also analyzed using either FTIR spectroscopy or gas chromatography (GC-FID). Methane emissions from seeps varied from approximately 7 to 54,000 g m-2 day-1, while emissions from soil degassing were between 0 and 9,000 g m-2 day-1. Total emissions were estimated to be in the order of 103 kg day-1 for methane, and at least 10 and 5 kg day-1 for ethane and propane, respectively. The seeping gas exhibited high C1/(C2 + C3) ratios, likely due to molecular fractionation during gas migration from a subsurface petroleum reservoir. Evidence for biodegredation in certain samples was indicated by large i-butane to n-butane ratios. These molecular alterations can be important tracers of natural seepage and should be considered in the atmospheric modelling of the relative contribution of fossil fuel (anthropogenic fugitive emission and natural geologic sources) vs biogenic sources, on local and global scales.

Characterization of Methane Degradation and Methane-Degrading Microbes in Alaska Coastal Water

Energy Technology Data Exchange (ETDEWEB)

Kirchman, David L. [Univ. of Delaware, Lewes, DE (United States)

2012-03-29

The net flux of methane from methane hydrates and other sources to the atmosphere depends on methane degradation as well as methane production and release from geological sources. The goal of this project was to examine methane-degrading archaea and organic carbon oxidizing bacteria in methane-rich and methane-poor sediments of the Beaufort Sea, Alaska. The Beaufort Sea system was sampled as part of a multi-disciplinary expedition (Methane in the Arctic Shelf or MIDAS) in September 2009. Microbial communities were examined by quantitative PCR analyses of 16S rRNA genes and key methane degradation genes (pmoA and mcrA involved in aerobic and anaerobic methane degradation, respectively), tag pyrosequencing of 16S rRNA genes to determine the taxonomic make up of microbes in these sediments, and sequencing of all microbial genes (metagenomes ). The taxonomic and functional make-up of the microbial communities varied with methane concentrations, with some data suggesting higher abundances of potential methane-oxidizing archaea in methane-rich sediments. Sequence analysis of PCR amplicons revealed that most of the mcrA genes were from the ANME-2 group of methane oxidizers. According to metagenomic data, genes involved in methane degradation and other degradation pathways changed with sediment depth along with sulfate and methane concentrations. Most importantly, sulfate reduction genes decreased with depth while the anaerobic methane degradation gene (mcrA) increased along with methane concentrations. The number of potential methane degradation genes (mcrA) was low and inconsistent with other data indicating the large impact of methane on these sediments. The data can be reconciled if a small number of potential methane-oxidizing archaea mediates a large flux of carbon in these sediments. Our study is the first to report metagenomic data from sediments dominated by ANME-2 archaea and is one of the few to examine the entire microbial assemblage potentially involved in

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

Science.gov (United States)

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

Science.gov (United States)

Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

2016-09-01

Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

Do we expand the petrochemical industry in Canada or sell our ethane/NGL south of the border?

International Nuclear Information System (INIS)

Schultz, J.

1996-01-01

The supply and demand for Canadian natural gas liquids (NGL) was discussed. For the supply issue, the CERI forecast showed that there will be growing surpluses of NGL in Canada with available incremental volumes increased from 26 Mb/d in 1995 to 74 Mb/d in 2005. The majority of this volume is ethane, which will not be extracted without new markets. The challenge for ethane is to find new pipeline opportunities that would provide better economics. If ethane is to be exported, new grassroots pipelines will have to be constructed. Evaluation of existing capacities, such as the Cochin and Interprovincial pipeline systems, should be the first logical step. A recent announcement of the Northern Area Transportation System (NATS), a natural gas pipeline from N.E. British Columbia to Chicago, was assessed. A new pipeline, however, was not considered feasible as long as the netback to producers or shippers after deducting the tariff is less than the netback received from current markets. It was concluded that the plentiful supply and extreme volatility in prices will make new pipeline projects difficult to market. Retaining ethane in Alberta for a growing petrochemicals industry appears to be, at least for the present, be a more acceptable alternative than shipping it to the US Gulf Coast. 8 figs

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

Science.gov (United States)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with

Gamma-induced reactions of bromo-ethane with olefines. Addition of ethyl radicals to hexene-1 and propylene

International Nuclear Information System (INIS)

Myshkin, V.E.; Shostenko, A.G.; Zagorets, P.A.; Pchelkin, A.I.; Markova, K.G.

1978-01-01

Radiation interaction of bromo-ethane with propylene and 1-hexene has been studied with the aim to investigate the action of γ-radiation on bromalkanes. The absorbed dose rate is 50 rad/s. The reaction products separated by preparative chromatography have been identified with infrared spectroscopy, elemental, chromatographic, and other physico-chemical methods of analysis. It has been established that the reaction with propylene gives rise to telomers whereas interaction of bromo-ethane with 1-hexene yields only the addition product (4-bromoctane). The activation energy of the reactions of adding ethyl radicals to 1-hexene and propylene has been found equal to (3.8+-0.4 kcal/mol) and (2.2+-0.2 kcal/mol), respectively. The activation energy of the reaction of chain transfer through bromo-ethane is (3.7+-0.3 kcal/mol.)

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

International Nuclear Information System (INIS)

Chandra, Sankhabrata; Bhattacharya, Atanu; Periyasamy, Ganga

2015-01-01

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH 2 , CF 3 , and COOH substituents) molecules paired with NH 3 (referred as ACl:NH 3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH 3 complex, the hole is predicted to migrate from the NH 3 -end to the ClCN-end of the NCCl⋯NH 3 complex in approximately 0.5 fs on the D 0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H 2 NCl:NH 3 , F 3 CCl:NH 3 , and HOOCCl:NH 3 , exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH 3 and HOCl:NH 3 complexes do not exhibit any charge migration following vertical ionization to the D 0 cation state, pointing to interesting halogen bond strength-dependent charge migration

First principles study of halogens adsorption on intermetallic surfaces

International Nuclear Information System (INIS)

Zhu, Quanxi; Wang, Shao-qing

2016-01-01

Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

Isostructurality and non-isostructurality in the series of halogenated organic crystal substances. The structure of Hal-aggregates

International Nuclear Information System (INIS)

Grineva, O.V.; Zorkij, P.M.

2001-01-01

Local characteristics and the type of intermolecular Hal-aggregates (ensembles of contacting halogen atoms of adjacent molecules) present in chemically similar halogenated crystal substances, differing only in the nature of Hal atoms, are compared. 23 series of halogenated hydrocarbons, including 57 crystal structures were considered. A clearly pronounced specificity of Hal-aggregates for compounds with a low and intermediate content of halogen was revealed. It was found that, as a rule, coordination number of Hal atom by Hal adjacent atoms increases in the series F-Cl-Br-I [ru

Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

Science.gov (United States)

Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

2015-12-01

Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

Halogens in pore water of peat bogs – the role of peat decomposition and dissolved organic matter

Directory of Open Access Journals (Sweden)

H. Biester

2006-01-01

Full Text Available Halogens are strongly enriched in peat and peatlands and such they are one of their largest active terrestrial reservoir. The enrichment of halogens in peat is mainly attributed to the formation of organohalogens and climatically controlled humification processes. However, little is known about release of halogens from the peat substrate and the distribution of halogens in the peat pore water. In this study we have investigated the distribution of chlorine, bromine and iodine in pore water of three pristine peat bogs located in the Magellanic Moorlands, southern Chile. Peat pore waters were collected using a sipping technique, which allows in situ sampling down to a depth greater than 6m. Halogens and halogen species in pore water were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in pore water are 15–30 times higher than in rainwater. Mean concentrations of chlorine, bromine and iodine in pore water were 7–15 mg l−1, 56–123 μg l−1, and 10–20 μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organobromine and organoiodine were the predominant species in pore waters, whereas chlorine in pore water was mostly chloride. Advection and diffusion of halogens were found to be generally low and halogen concentrations appear to reflect release from the peat substrate. Release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. It has been concluded that the release of halogenated dissolved organic matter (DOM is the predominant mechanism of iodine and bromine release from peat.

Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

Energy Technology Data Exchange (ETDEWEB)

Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

2016-02-28

Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

Energy Technology Data Exchange (ETDEWEB)

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

Efficient 1.5-μm Raman generation in ethane-filled hollow-core fiber

Science.gov (United States)

Chen, Yubin; Gu, Bo; Wang, Zefeng; Lu, Qisheng

2016-11-01

We demonstrated for the first time a novel and effective method for obtaining both high peak-power and narrow linewidth 1.5 μm fiber sources through gas Raman effect in hollow core fibers. An Ethane-filled ice-cream antiresonance hollow-core fiber is pumped with a high peak-power pulse 1064 nm microchip laser, generating 1552.7 nm Stokes wave by pure vibrational stimulated Raman scattering of ethane molecules. A maximum peak-power of about 400 kW is achieved with 6 meter fiber length at 2 bar pressure, and the linewidth is about 6.3 GHz. The maximum Raman conversion efficiency of 1064 nm to 1552.7 nm is about 38%, and the corresponding laser slope efficiency is about 61.5%.

Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

Science.gov (United States)

Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

2014-01-01

The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

Fragrance material review on 1-(2,5,5-trimethylcycloheptyl)ethan-1-one.

Science.gov (United States)

Scognamiglio, J; Letizia, C S; Api, A M

2013-12-01

A toxicologic and dermatologic review of 1-(2,5,5-trimethylcycloheptyl)ethan-1-one when used as a fragrance ingredient is presented. 1-(2,5,5-Trimethylcycloheptyl)ethan-1-one is a member of the fragrance structural group Alkyl Cyclic Ketones. These fragrances can be described as being composed of an alkyl, R1, and various substituted and bicyclic saturated or unsaturated cyclic hydrocarbons, R2, in which one of the rings may include up to 12 carbons. Alternatively, R2 may be a carbon bridge of C2-C4 carbon chain length between the ketone and cyclic hydrocarbon. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 1-(2,5,5-trimethylcycloheptyl)ethan-1-one were evaluated then summarized and includes physical properties, skin irritation, mucous membrane (eye) irritation, and skin sensitization data. A safety assessment of the entire Alkyl Cyclic Ketones will be published simultaneously with this document; please refer to Belsito et al. (Belsito, D., Bickers, D., Bruze, M., Calow, P., Dagli, M., Fryer, A.D., Greim, H., Miyachi, Y., Saurat, J.H., Sipes, I.G., 2013. A toxicologic and dermatologic assessment of alkyl cyclic ketones when used as fragrance ingredients. (submitted for publication)) for an overall assessment of the safe use of this material and all Alkyl Cyclic Ketones in fragrances. Copyright © 2013. Published by Elsevier Ltd.

Ethane ocean on Titan

Science.gov (United States)

Lunine, J. I.; Stevenson, D. J.; Yung, Y.L.

1983-01-01

Voyager I radio occultation data is employed to develop a qualitative model of an ethane ocean on Titan. It is suggested that the ocean contains 25 percent CH4 and that the ocean is in dynamic equilibrium with an N2 atmosphere. Previous models of a CH4 ocean are discounted due to photolysis rates of CH4 gas. Tidal damping of Titan's orbital eccentricity is taken as evidence for an ocean layer approximately 1 km deep, with the ocean floor being covered with a solid C2H2 layer 100 to 200 m thick. The photolytic process disrupting the CH4, if the estimates of the oceanic content of CH4 are correct, could continue for at least one billion years. Verification of the model is dependent on detecting CH4 clouds in the lower atmosphere, finding C2H6 saturation in the lower troposphere, or obtaining evidence of a global ocean.

Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

Science.gov (United States)

Wang, David T; Gruen, Danielle S; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C; Holden, James F; Hristov, Alexander N; Pohlman, John W; Morrill, Penny L; Könneke, Martin; Delwiche, Kyle B; Reeves, Eoghan P; Sutcliffe, Chelsea N; Ritter, Daniel J; Seewald, Jeffrey S; McIntosh, Jennifer C; Hemond, Harold F; Kubo, Michael D; Cardace, Dawn; Hoehler, Tori M; Ono, Shuhei

2015-04-24

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. Copyright © 2015, American Association for the Advancement of Science.

Improved processes of light hydrocarbon separation from LNG with its cryogenic energy utilized

International Nuclear Information System (INIS)

Gao Ting; Lin Wensheng; Gu Anzhong

2011-01-01

Research highlights: → We propose two new light hydrocarbon separation processes utilizing LNG cold energy. → Both processes produce liquefied ethane and LPG with high ethane recovery rate. → CH 4 -riched gas from the high pressure process is compressed to final pressure. → Re-liquefied CH 4 -riched gas from the low pressure one is pumped to final pressure. → Both processes have good performance; the low pressure one is economically better. -- Abstract: Liquefied natural gas (LNG) often consists of some kinds of light hydrocarbons other than methane, such as ethane, propane and butane, which are of high additional value. By efficiently utilization of LNG cryogenic energy, these light hydrocarbons (C 2 + ) can be separated from LNG with low power consumption and LNG is gasified meanwhile. Two novel light hydrocarbon separation processes are proposed in this paper. The first process uses a demethanizer working at higher pressure (about 4.5 MPa). The methane-riched natural gas from the demethanizer can be compressed to pipeline pressure with low power consumption. The other one uses a demethanizer working at lower pressure (about 2.4 MPa). By cascade utilization of LNG cryogenic energy, the methane-riched natural gas from the demethanizer is entirely re-liquefied. Then the liquid product is pressurized to pipeline pressure by pumps instead of compressors, reducing the power consumption greatly. By both of the two processes, liquefied ethane and LPG (liquefied petroleum gas, i.e. C 3 + ) at atmosphere pressure can be obtained directly, and high ethane recovery rate can be gained. On the basis of one typical feed gas composition, the effects of the ethane content and the ethane price to the economics of the light hydrocarbon separation plants are studied, and the economics are compared for these two processes. The results show that recovering light hydrocarbons from LNG can gain great profits by both of the two processes, and from the view of economics, the

Development of halogen-free, heat-resistant, low-voltage wire for automotive use

International Nuclear Information System (INIS)

Ueno, Keiji; Suzuki, Sizuo; Takahagi, Masatoshi; Uda, Ikujiro

1995-01-01

The environmental load of our motorized society is of major concern, and includes considerations of recycling of automotive parts as the industrial wastes. The total average length of AV, AVX (electrical wire insulated with PVC, cross-linked PVC), and AEX (electrical wire insulated with cross-linked polyolefin) wires required for the harnesses in modern automobiles is approximately 2,000-3,000 meters per unit. However these electrical wires contain a large amount of halogen, which can generate the smoke and corrosive gas. In response to this problem the authors have developed the electron beam irradiated halogen-free, heat-resistant, low-voltage electrical wire which does not contain any halogen based polymer or flame retardants. The developed wire features the reliability equivalent to AEX wire with minimum environmental load. (Author)

The biological fate of decabromodiphenyl ethane following oral, dermal or intravenous administration

Science.gov (United States)

1. The disposition of decabromodiphenyl ethane (DBDPE) was investigated based on concerns over its structural similarities to decaBDE, high potential for environmental persistence & bioaccumulation, and high production volume. 2. In the present study, female Sprague Dawley rats w...

(μ-Ethane-1,1,2,2-tetracarboxylatobis[tetraaquamanganese(II

Directory of Open Access Journals (Sweden)

Meng-Wei Xue

2011-04-01

Full Text Available In the centrosymmetric title molecule, [Mn2(C6H2O8(H2O8], the MnII atom is in an octahedral environment coordinated by six O-atom donors from water molecules and ethane-1,1,2,2-tetracarboxylate ligands. The crystal structure features a three-dimensional hydrogen-bonding network based on a strong and distinctive pattern of O—H...O hydrogen-bonding interactions.

Technetium (tin) ethane-1-hydroxy-1, 1-diphosphonate complexes

International Nuclear Information System (INIS)

Brand, J.A.G.M.

1981-10-01

The aim of this thesis is to establish the experimental conditions for the optimal preparation of the sup(99m)Tc(Sn)EHDP bone scanning agent. The pH and the concentrations of EHDP (ethane-1-hydroxy-1,1-disodium diphosphonate) and of Sn(II) may affect the yield and the biodistribution of the radiopharmacon. The investigation of the influence of these parameters is the subject of this investigation. (Auth.)

The biological fate of decabromodiphenyl ethane following ...

Science.gov (United States)

1. The disposition of decabromodiphenyl ethane (DBDPE) was investigated based on concerns over its structural similarities to decaBDE, high potential for environmental persistence & bioaccumulation, and high production volume. 2. In the present study, female Sprague Dawley rats were administered a single dose of [14C]-DBDPE by oral, topical, or IV routes. Another set of rats were administered 10 daily oral doses of 14C]-DBDPE. Male B6C3F1/Tac mice were administered a single oral dose.3. DBDPE was poorly absorbed following oral dosing, with 95% of administered [14C]-radioactivity recovered in the feces, 1% recovered in the urine and less than 3% in the tissues at 72 h. DBDPE excretion was similar in male mice and female rats. Accumulation of [14C]-DBDPE was observed in liver and the adrenal gland after 10 daily oral doses.4. The dermis acted as a depot for dermally applied DBDPE; conservative estimates predict approx. 14 ± 8% of DBDPE may be absorbed into human skin in vivo; approx. 7 ± 4% of the parent chemical is expected to reach systemic circulation following continuous exposure (24 h). 5. Following intravenous administration, 6% of the dose was recovered in urine and 28% in the feces, while ~70% of the dose remained in tissues after 72 hours, with the highest concentrations found in the liver (42%) and lung (17%). Decabromodiphenyl ethane (DBDPE) is an additive brominated flame retardant used in a variety commercial products. It has been detected in indo

Recoil halogen reactions in liquid and frozen aqueous solutions of biomolecules

International Nuclear Information System (INIS)

Arsenault, L.J.; Blotcky, A.J.; Firouzbakht, M.L.; Rack, E.P.; Nebraska Univ., Omaha

1982-01-01

Reactions of recoil 38 Cl, 80 Br and 128 I have been studied in crystalline systems of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as well as liquid and frozen aqueous solutions of these halogenated biomolecules. In all systems expect crystalline 5-iuodouracil the major product was the radio-labelled halide ion. There was no evidence for other halogen inorganic species. The major labelled organic product was the parent molecule. A recoil atom tracer technique was developed to acquire site information of the biomolecule solutes in the liquid and frozen aqueous systems. For all liquid and frozen aqueous systems, the halogenated biomolecules tended to aggregate. For liquid systems, the tendency for aggregation diminished as the solute concentration approached zero, where the probable state of the solute approached a monomolecular dispersion. Unlike the liquid state, the frozen ice lattice demonstated a ''caging effect'' for the solute aggregates which resulted in constant product yields over the whole concentration range. (orig.)

Environmental levels and toxicological potencies of a novel mixed halogenated carbazole

Directory of Open Access Journals (Sweden)

Miren Pena-Abaurrea

2016-09-01

Full Text Available The present work involves an extensive analytical and toxicological description of a recently identified mixed halogenated carbazole found in sediment samples, 1,8-dibromo-3,6-dichloro-9H-carbazole (BCCZ. Concentrations and the relative effect potency (REP were calculated for the target BCCZ in a set of stream sediments collected in 2008 in Ontario, Canada. The levels calculated for BCCZ as compared to those previously assessed for legacy persistent organic pollutants (POPs in the same samples revealed a significant contribution of BCCZ to the total organic chemical contamination (<1%–95%; average 37%. The corresponding dioxin toxic equivalencies (TEQs of BCCZ in the sediment extracts were estimated from experimental REP data. The experimental data presented supports the classification of this emerging halogenated chemical as a contaminant of emerging environmental concern. Although potential emission sources could not be identified, this study highlights the importance of on-going research for complete characterization of halogenated carbazoles and related compounds.

Development of no halogen incombustible cables for atomic energy

International Nuclear Information System (INIS)

Ishii, Nobumasa; Kimura, Hitoshi; Fujimura, Shun-ichi

1990-01-01

In upgrading light water reactor technology, it is important to improve the reliability of machinery and equipment, to make regular inspection efficient, to extend the period of continuous operation, to optimize operation cycle and to improve the maintainability of plant facilities. For the cables for nuclear power stations, high incombustibility is required, and at present halogen system incombustible materials are used. Recently the development of no halogen incombustible cables has been advanced, with which the generation of corrosive gas and smoke at the time of fires is slight. In this study, the application of such no halogen incombustible cables to nuclear power stations and the improvement of reliability of the cables were investigated. The cables to be developed are those for electric power, control and instrumentation in BWR plants and insulated electric wires. The required characteristics are incombustibility, no generation of smoke and corrosive gas at the time of fires, radiation resistance and steam resistance in LOCA. The selection of base polymers, metal hydrates and radiation protectors, the evaluation of radiation resistance and steam resistance, the examination of the corrosive and poisonous properties of generated gas and smoke generation and so on are reported. The development was successful. (K.I.)

Mechanism of the flame ionization detector. II. Isotope effects and heteroatom effects

DEFF Research Database (Denmark)

Holm, Torkil

1997-01-01

reactions in the hydrogen flame of compounds added to the hydrogen gas in low concentrations were followed. Alcohols, ethers, ketones, and esters all produced methane and carbon monoxide, while amines produced methane and hydrogen cyanide, halogen compounds methane and hydrogen halide, etc. The FID response...

Baseline Geochemistry of Natural Occurring Methane and Saline Groundwater in an Area of Unconventional Shale Gas Development Through Time

Science.gov (United States)

Harkness, J.; Darrah, T.; Warner, N. R.; Whyte, C. J.; Moore, M. T.; Millot, R.; Kloppmann, W.; Jackson, R. B.; Vengosh, A.

2017-12-01

Naturally occurring methane is nearly ubiquitous in most sedimentary basins and delineating the effects of anthropogenic contamination sources from geogenic sources is a major challenge for evaluating the impact of unconventional shale gas development on water quality. This study employs a broadly integrated study of various geochemical techniques to investigate the geochemical variations of groundwater and surface water before, during, and after hydraulic fracturing.This approache combines inorganic geochemistry (major cations and anions), stable isotopes of select inorganic constituents including strontium (87Sr/86Sr), boron (δ11B), lithium (δ7Li), and carbon (δ13C-DIC), select hydrocarbon molecular (methane, ethane, propane, butane, and pentane) and isotopic tracers (δ13C-CH4, δ13C-C2H6), tritium (3H), and noble gas elemental and isotopic composition (He, Ne, Ar) to apportion natural and anthropogenic sources of natural gas and salt contaminants both before and after drilling. Methane above 1 ccSTP/L in groundwater samples awas strongly associated with elevated salinity (chloride >50 mg/L).The geochemical and isotopic analysis indicate saline groundwater originated via naturally occurring processes, presumably from the migration of deeper methane-rich brines that have interacted extensively with coal lithologies. The chemistry and gas compostion of both saline and fresh groundwater wells did not change following the installation of nearby shale-gas wells.The results of this study emphasize the value of baseline characterization of water quality in areas of fossil fuel exploration. Overall this study presents a comprehensive geochemical framework that can be used as a template for assessing the sources of elevated hydrocarbons and salts to water resources in areas potentially impacted by oil and gas development.

Chlorine dioxide as phenol and H2S scavenger - formation of halogenated phenols and subsequent environmental risk

Energy Technology Data Exchange (ETDEWEB)

Melbye, Alf G.; Faksness, Liv-Guri; Knudsen, Boerre Leif

2006-03-15

Formation of halogenated phenols as side products from treatment of produced water with aqueous chlorine dioxide has been investigated. The literature describes formation of halogenated hydrocarbons in effluent treatment using chlorine, hypochlorite and chlorine dioxide. A new chlorine dioxide product, originally intended as a H2S scavenger in the oil and gas industry, has been tested both as a phenol scavenger and H2S-scavenger for produced water applications. The concern about the possible formation of halogenated by-products initiated laboratory testing of chlorine dioxide as phenol and H2S scavenger for produced water applications. The tests also included synthetic matrixes containing phenols, and the tests show that halogenated phenols, mainly brominated species, are found in produced water after treatment with chlorine dioxide. Due to potential environmental risk from halogenated organic contaminants, the use of chlorine dioxide as phenol and H2S scavenger is not recommended. (Author)

Determination of N-containing halogenated natural products using gas chromatography in combination of a nitrogen-phosphorus-detector

Energy Technology Data Exchange (ETDEWEB)

Melcher, J.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie

2004-09-15

In the last few years several nonpolar halogenated natural products (HNPs) such as Q1, MHC-1, BC-2, BC-3, BC-10 were detected at elevated concentrations in marine biota samples. In addition, there are still some abundant peaks of halogenated compounds frequently found in the gas chromatograms of many marine samples which have not yet been identified. Some of the known halogenated natural products (Q1, HDBPs including BC-10, bromoindoles) contain N-heterocyclic backbones. Since nitrogen is scarcely found in anthropogenic halogenated compounds, the detection of N-containing halogenated substances may be used as a first indicator for the presence of HNPs in a sample extract. In the presented method we studied the suitability of a nitrogen phosphorous detector (NPD) for quantification of Q1 and the detection of Ncontaining compounds in marine biota. Analyses were accompanied with GC/ECD analyses.

A 19F NMR study of C-I....pi- halogen bonding

DEFF Research Database (Denmark)

Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.

2011-01-01

The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

Science.gov (United States)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

Science.gov (United States)

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

Czech Academy of Sciences Publication Activity Database

Riley, Kevin Eugene; Murray, J. S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P.

2013-01-01

Roč. 19, č. 11 (2013), s. 4651-4659 ISSN 1610-2940 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : dispersion * electrostatics * halogen bonding * noncovalent interactions Subject RIV: CE - Biochemistry Impact factor: 1.867, year: 2013

Demonstration of a Fast, Precise Propane Measurement Using Infrared Spectroscopy

Science.gov (United States)

Zahniser, M. S.; Roscioli, J. R.; Nelson, D. D.; Herndon, S. C.

2016-12-01

Propane is one of the primary components of emissions from natural gas extraction and processing activities. In addition to being an air pollutant, its ratio to other hydrocarbons such as methane and ethane can serve as a "fingerprint" of a particular facility or process, aiding in identifying emission sources. Quantifying propane has typically required laboratory analysis of flask samples, resulting in low temporal resolution and making plume-based measurements infeasible. Here we demonstrate fast (1-second), high precision (infrared spectroscopy at 2967 wavenumbers. In addition, we explore the impact of nearby water and ethane absorption lines on the accuracy and precision of the propane measurement. Finally, we discuss development of a dual-laser instrument capable of simultaneous measurements of methane, ethane, and propane (the C1-C3 compounds), all within a small spatial package that can be easily deployed aboard a mobile platform.

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

Science.gov (United States)

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

NARCIS (Netherlands)

Lamont, C.A.; Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, T.W.L.; Andriessen, R.; Groen, P.

2015-01-01

For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses

Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

Science.gov (United States)

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

Near-infrared incoherent broadband cavity enhanced absorption spectroscopy (NIR-IBBCEAS) for detection and quantification of natural gas components.

Science.gov (United States)

Prakash, Neeraj; Ramachandran, Arun; Varma, Ravi; Chen, Jun; Mazzoleni, Claudio; Du, Ke

2018-06-28

The principle of near-infrared incoherent broadband cavity enhanced absorption spectroscopy was employed to develop a novel instrument for detecting natural gas leaks as well as for testing the quality of natural gas mixtures. The instrument utilizes the absorption features of methane, butane, ethane, and propane in the wavelength region of 1100 nm to 1250 nm. The absorption cross-section spectrum in this region for methane was adopted from the HITRAN database, and those for the other three gases were measured in the laboratory. A singular-value decomposition (SVD) based analysis scheme was employed for quantifying methane, butane, ethane, and propane by performing a linear least-square fit. The developed instrument achieved a detection limit of 460 ppm, 141 ppm, 175 ppm and 173 ppm for methane, butane, ethane, and propane, respectively, with a measurement time of 1 second and a cavity length of 0.59 m. These detection limits are less than 1% of the Lower Explosive Limit (LEL) for each gas. The sensitivity can be further enhanced by changing the experimental parameters (such as cavity length, lamp power etc.) and using longer averaging intervals. The detection system is a low-cost and portable instrument suitable for performing field monitorings. The results obtained on the gas mixture emphasize the instrument's potential for deployment at industrial facilities dealing with natural gas, where potential leaks pose a threat to public safety.

Sorption Hysteresis of Light Hydrocarbons and Carbon Dioxide in Shale and Kerogen

KAUST Repository

Zhao, Huangjing; Lai, Zhiping; Firoozabadi, Abbas

2017-01-01

We present adsorption and desorption isotherms of methane, ethane, propane, n-butane and iso-butane as well as carbon dioxide for two shales and isolated kerogens determined by a gravimetric method. The sorption measurements of two shales were performed at three different temperatures, 308.15, 323.15, and 338.15 K. For the isolated kerogens, the measurements were conducted at 338.15 K. Methane and ethane sorption isotherms were measured to 35 bar. Carbon dioxide sorption isotherms were studied to 30 bar. Due to the low vapor pressure at room temperature, the sorption isotherms of propane, n-butane and iso-butane were measured to 8, 2, and 2 bar, respectively. The adsorptions of propane, n-butane, and iso-butane were much higher than methane at the highest pressures where the measurements were conducted. The adsorption of n-butane was 10 times higher than methane by mole at 2 bar, followed by iso-butane and propane. Our data show significant adsorption hysteresis in ethane, propane, n-butane and iso-butane. The most pronounced hysteresis was found in n-butane and iso-butane. Significant hysteresis is attributed to the reversible structural changes of kerogens. Dissolution of adsorbates into organic matter may also affect the hysteresis. This is the first report of propane and butane sorption isotherms in shales.

Sorption Hysteresis of Light Hydrocarbons and Carbon Dioxide in Shale and Kerogen

KAUST Repository

Zhao, Huangjing

2017-11-20

We present adsorption and desorption isotherms of methane, ethane, propane, n-butane and iso-butane as well as carbon dioxide for two shales and isolated kerogens determined by a gravimetric method. The sorption measurements of two shales were performed at three different temperatures, 308.15, 323.15, and 338.15 K. For the isolated kerogens, the measurements were conducted at 338.15 K. Methane and ethane sorption isotherms were measured to 35 bar. Carbon dioxide sorption isotherms were studied to 30 bar. Due to the low vapor pressure at room temperature, the sorption isotherms of propane, n-butane and iso-butane were measured to 8, 2, and 2 bar, respectively. The adsorptions of propane, n-butane, and iso-butane were much higher than methane at the highest pressures where the measurements were conducted. The adsorption of n-butane was 10 times higher than methane by mole at 2 bar, followed by iso-butane and propane. Our data show significant adsorption hysteresis in ethane, propane, n-butane and iso-butane. The most pronounced hysteresis was found in n-butane and iso-butane. Significant hysteresis is attributed to the reversible structural changes of kerogens. Dissolution of adsorbates into organic matter may also affect the hysteresis. This is the first report of propane and butane sorption isotherms in shales.

Matrimid® derived carbon molecular sieve hollow fiber membranes for ethylene/ethane separation

KAUST Repository

Xu, Liren; Rungta, Meha; Koros, William J.

2011-01-01

materials in realistic gas separations. The very challenging ethylene/ethane separation is the primary target of this work. Matrimid® derived CMS hollow fiber membranes have been investigated in this work. Resultant CMS fiber showed interesting separation

Model study of multiphase DMS oxidation with a focus on halogens

Directory of Open Access Journals (Sweden)

R. von Glasow

2004-01-01

Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

Science.gov (United States)

Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

2016-07-01

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

KAUST Repository

Ward, Jeremy W.

2014-05-15

Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin-film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin-film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X-ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 dw, where dw represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting "edge-on" versus "face-on" molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the "edge-on" self-assembly of molecules forms uniform, (001) lamellar-textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the "face-on" oriented crystallites increases. The role of interfacial halogenation in mediating texture formation and the self-patterning of organic semiconductor films, as well as the resulting effects on charge transport in organic thin-film transistors, are explored. The presence of two or more anchoring sites between a halogenated semiconductor and a halogenated self-assembled monolayer, closer than about twice the corresponding van der Waals distance, alter the microstructure and improve electrical properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methane production and methane consumption: a review of processes underlying wetland methane fluxes.

NARCIS (Netherlands)

Segers, R.

1998-01-01

Potential rates of both methane production and methane consumption vary over three orders of magnitude and their distribution is skew. These rates are weakly correlated with ecosystem type, incubation temperature, in situ aeration, latitude, depth and distance to oxic/anoxic interface. Anaerobic

POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN OPPOSED FLOW DIFFUSION FLAMES OF ETHANE. (R825412)

Science.gov (United States)

AbstractThe effect of fuel-side carbon density on the levels of polycyclic aromatic hydrocarbon (PAH) formation in atmospheric pressure, opposed flow, ethane diffusion flames has been studied using heated micro-probe sampling and gas chromatography/mass spectrometry (...

Increased breath ethane levels in medicated patients with schizophrenia and bipolar disorder are unrelated to erythrocyte omega-3 fatty acid abundance.

Science.gov (United States)

Ross, Brian M; Maxwell, Ross; Glen, Iain

2011-03-30

Oxidative stress has been reported to be elevated in mental illness. Preliminary evidence suggests this phenomenon can be assessed non-invasively by determining breath levels of the omega-3 polyunsaturated fatty acid (PUFA) oxidation product ethane. This study compares alkane levels in chronic, medicated, patients with schizophrenia or bipolar disorder with those in healthy controls. Both ethane and butane levels were significantly increased in patients with schizophrenia or bipolar disorder, although elevated butane levels were likely due to increased ambient gas concentrations. Ethane levels were not correlated with symptom severity or with erythrocyte omega-3 PUFA levels. Our results support the hypothesis that oxidative stress is elevated in patients with schizophrenia and bipolar disorder leading to increased breath ethane abundance. This does not appear to be caused by increased abundance of omega-3 PUFA, but rather is likely due to enhanced oxidative damage of these lipids. As such, breath hydrocarbon analysis may represent a simple, non-invasive means to monitor the metabolic processes occurring in these disorders. Copyright © 2010 Elsevier Inc. All rights reserved.

Ethane in Planetary and Cometary Atmospheres: Transmittance and Fluorescence Models of the nu7 Band at 3.3 Micrometers

Science.gov (United States)

Villanueva, G. L.; Mumma, M. J.; Magee-Sauer, K.

2011-01-01

Ethane and other hydrocarbon gases have strong rovibrational transitions in the 3.3 micron spectral region owing to C-H, CH2, and CH3 vibrational modes, making this spectral region prime for searching possible biomarker gases in extraterrestrial atmospheres (e.g., Mars, exoplanets) and organic molecules in comets. However, removing ethane spectral signatures from high-resolution terrestrial transmittance spectra has been imperfect because existing quantum mechanical models have been unable to reproduce the observed spectra with sufficient accuracy. To redress this problem, we constructed a line-by-line model for the n7 band of ethane (C2H6) and applied it to compute telluric transmittances and cometary fluorescence efficiencies. Our model considers accurate spectral parameters, vibration-rotation interactions, and a functional characterization of the torsional hot band. We integrated the new band model into an advanced radiative transfer code for synthesizing the terrestrial atmosphere (LBLRTM), achieving excellent agreement with transmittance data recorded against Mars using three different instruments located in the Northern and Southern hemispheres. The retrieved ethane abundances demonstrate the strong hemispheric asymmetry noted in prior surveys of volatile hydrocarbons. We also retrieved sensitive limits for the abundance of ethane on Mars. The most critical validation of the model was obtained by comparing simulations of C2H6 fluorescent emission with spectra of three hydrocarbon-rich comets: C/2004 Q2 (Machholz), 8P/Tuttle, and C/2007 W1 (Boattini). The new model accurately describes the complex emission morphology of the nu7 band at low rotational temperatures and greatly increases the confidence of the retrieved production rates (and rotational temperatures) with respect to previously available fluorescence models.

Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

Energy Technology Data Exchange (ETDEWEB)

Skinner, G.A.; Parker, L.E.; Marshall, P.J.

1978-01-01

Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

Study of the halogenation of EuBa[sub 2]Cu[sub 3]O[sub 6]. Etude de l'halogenation de EuBa[sub 2]Cu[sub 3]O[sub 6

Energy Technology Data Exchange (ETDEWEB)

Kabeya, D.T. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Mokhtari, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Perrin, C. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Sergent, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Grushko, Yu. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Kokovina, L. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Rozhniakova, N. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.)

1994-11-01

Sintered samples of EuBa[sub 2]Cu[sub 3]O[sub 6] have been halogenated at low temperature (t<300 C) by treatments under NF[sub 3] or CCl[sub 4] flow diluted in nitrogen, or by reaction with iodine in sealed tubes. Such mild conditions of synthesis allowed to avoid the decomposition of the material during the reactions. The incorporation of the halogen in the sample has been evidenced by the weight gain, by the evolution of the unit-cell parameters and by SEM and EDS analyses. After fluorination and chlorination, the samples become superconducting, but no superconducting behaviour is observed after iodination. These results are compared to the ones previously obtained during the halogenation of YBa[sub 2]Cu[sub 3]O[sub 6]. (orig.).

Prediction of vapour-liquid and vapour-liquid-liquid equilibria of nitrogen-hydrocarbon mixtures used in J-T refrigerators

Science.gov (United States)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

Nitrogen-hydrocarbon mixtures are widely used as refrigerants in J-T refrigerators operating with mixtures, as well as in natural gas liquefiers. The Peng-Robinson equation of state has traditionally been used to simulate the above cryogenic process. Multi parameter Helmholtz energy equations are now preferred for determining the properties of natural gas. They have, however, been used only to predict vapour-liquid equilibria, and not vapour-liquid-liquid equilibria that can occur in mixtures used in cryogenic mixed refrigerant processes. In this paper the vapour-liquid equilibrium of binary mixtures of nitrogen-methane, nitrogen-ethane, nitrogen-propane, nitrogen-isobutane and three component mixtures of nitrogen-methane-ethane and nitrogen-methane-propane have been studied with the Peng-Robinson and the Helmholtz energy equations of state of NIST REFPROP and compared with experimental data available in the literature.

UARS Halogen Occultation Experiment (HALOE) Level 2 V001

Data.gov (United States)

National Aeronautics and Space Administration — The HALOE home page on the WWW is http://haloe.gats-inc.com/home/index.php The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

International Nuclear Information System (INIS)

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing; Bai, Hongcun

2015-01-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M 2 (CN) 5 ] −1 (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca 2 (CN) 5 ] −1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

Energy Technology Data Exchange (ETDEWEB)

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing, E-mail: rayinyin@nwu.edu.cn [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Bai, Hongcun [Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Tunable Diode Laser Absorption Spectroscopy Sensor for Calibration Free Humidity Measurements in Pure Methane and Low CO2 Natural Gas.

Science.gov (United States)

Nwaboh, Javis Anyangwe; Pratzler, Sonja; Werhahn, Olav; Ebert, Volker

2017-05-01

We report a new direct tunable diode laser absorption spectroscopy (dTDLAS) sensor for absolute measurements of H 2 O in methane, ethane, propane, and low CO 2 natural gas. The sensor is operated with a 2.7 µm DFB laser, equipped with a high pressure single pass gas cell, and used to measure H 2 O amount of substance fractions in the range of 0.31-25 000 µmol/mol. Operating total gas pressures are up to 5000 hPa. The sensor has been characterized, addressing the traceability of the spectrometric results to the SI and the evaluation of the combined uncertainty, following the guide to the expression of uncertainty in measurement (GUM). The relative reproducibility of H 2 O amount of substance fraction measurements at 87 µmol/mol is 0.26% (0.23 µmol/mol). The maximum precision of the sensor was determined using a H 2 O in methane mixture, and found to be 40 nmol/mol for a time resolution of 100 s. This corresponds to a normalized detection limit of 330 nmol mol -1 ·m Hz -1/2 . The relative combined uncertainty of H 2 O amount fraction measurements delivered by the sensor is 1.2%.

Self-assembly of iodine in superfluid helium droplets. Halogen bonds and nanocrystals

Energy Technology Data Exchange (ETDEWEB)

He, Yunteng; Zhang, Jie; Lei, Lei; Kong, Wei [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

2017-03-20

We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Aa, much closer to the value of 3.5 Aa in iodine crystals than to the van der Waals distance of 4.3 Aa. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi-layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

KAUST Repository

Li, Baiyan

2014-06-18

In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

Introduction of π-complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane

KAUST Repository

Li, Baiyan; Zhang, Yiming; Krishna, Rajamani; Yao, Kexin; Han, Yu; Wu, Zili; Ma, Dingxuan; Shi, Zhan; Pham, Tony T.; Space, Brian; Liu, Jian; Thallapally, Praveen K.; Liu, Jun; Chrzanowski, Matthew; Ma, Shengqian

2014-01-01

In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO 3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C 2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane. © 2014 American Chemical Society.

Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials.

Science.gov (United States)

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Hoefman, Sven; De Vos, Paul; Boeckx, Pascal; Boon, Nico

2014-04-01

Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (~20 % (v/v)) and low (~100 ppmv) methane mixing ratios. Methylocystis parvus in autoclaved aerated concrete (AAC) exhibited the highest methane removal rate at high (28.5 ± 3.8 μg CH₄ g⁻¹ building material h⁻¹) and low (1.7 ± 0.4 μg CH₄ g⁻¹ building material h⁻¹) methane mixing ratio. Due to the higher volume of pores with diameter >5 μm compared to other materials tested, AAC was able to adsorb more bacteria which might explain for the higher methane removal observed. The total methane and carbon dioxide-carbon in the headspace was decreased for 65.2 ± 10.9 % when M. parvus in Ytong was incubated for 100 h. This study showed that immobilized MOB on building materials could be used to remove methane from the air and also act as carbon sink.

Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

Science.gov (United States)

Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

2008-10-30

A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

KAUST Repository

Zhu, Haibo

2015-03-05

The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

Unprecedented twofold intramolecular hydroamination in diam(m)ine-dicarboxylatodichloridoplatinum(IV) complexes - ethane-1,2-diamine vs. ammine ligands.

Science.gov (United States)

Reithofer, Michael R; Galanski, Markus; Arion, Vladimir B; Keppler, Bernhard K

2008-03-07

Reaction of (OC-6-13)-bis(2Z-3-carboxyacrylato)dichlorido(ethane-1,2-diamine)platinum(IV) and (OC-6-13)-diamminebis(2Z-3-carboxyacrylato)dichloridoplatinum(IV) with propylamine in the presence of 1,1'-carbonyl diimidazole afforded not the expected amides; instead, beside amide formation, a twofold intramolecular attack of the am(m)ine ligand at the C[double bond, length as m-dash]C bonds was observed involving either both (ethane-1,2-diamine) or only one (ammine) coordinated nitrogen atom(s).

Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

Institute of Scientific and Technical Information of China (English)

WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

2007-01-01

Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N＞O＞S; O(sp3)＞O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

Science.gov (United States)

Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

2015-08-03

Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rain increases methane production and methane oxidation in a boreal thermokarst bog

Science.gov (United States)

Neumann, R. B.; Moorberg, C.; Turner, J.; Wong, A.; Waldrop, M. P.; Euskirchen, E. S.; Edgar, C.; Turetsky, M. R.

2017-12-01

Bottom-up biogeochemical models of wetland methane emissions simulate the response of methane production, oxidation and transport to wetland conditions and environmental forcings. One reason for mismatches between bottom-up and top-down estimates of emissions is incomplete knowledge of factors and processes that control microbial rates and methane transport. To advance mechanistic understanding of wetland methane emissions, we conducted a multi-year field investigation and plant manipulation experiment in a thermokarst bog located near Fairbanks, Alaska. The edge of the bog is experiencing active permafrost thaw, while the center of the bog thawed 50 to 100 years ago. Our study, which captured both an average year and two of the wettest years on record, revealed how rain interacts with vascular vegetation and recently thawed permafrost to affect methane emissions. In the floating bog, rain water warmed and oxygenated the subsurface, but did not alter soil saturation. The warmer peat temperatures increased both microbial methane production and plant productivity at the edge of the bog near the actively thawing margin, but minimally altered microbial and plant activity in the center of the bog. These responses indicate processes at the edge of the bog were temperature limited while those in the center were not. The compounding effect of increased microbial activity and plant productivity at the edge of the bog doubled methane emissions from treatments with vascular vegetation during rainy years. In contrast, methane emissions from vegetated treatments in the center of the bog did not change with rain. The oxygenating influence of rain facilitated greater methane oxidation in treatments without vascular vegetation, which offset warming-induced increases in methane production at the edge of the bog and decreased methane emissions in the center of the bog. These results elucidate the complex and spatially variable response of methane production and oxidation in

Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules

Czech Academy of Sciences Publication Activity Database

Řezáč, Jan; Riley, Kevin Eugene; Hobza, Pavel

2012-01-01

Roč. 8, č. 11 (2012), s. 4285-4292 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : halogenated molecules * noncovalent interactions * benchmark calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

Polar Flattening and the Strength of Halogen Bonding

Czech Academy of Sciences Publication Activity Database

Sedlák, Robert; Kolář, Michal H.; Hobza, Pavel

2015-01-01

Roč. 11, č. 10 (2015), s. 4727-4732 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * interaction energies * halogen bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

Directory of Open Access Journals (Sweden)

GAO Shan

2017-12-01

Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

Isomorphism of 2-methylnaphthalene and 2-halonaphthalenes as a revealer of a special interaction between methyl and halogen

Science.gov (United States)

Calvet, T.; Cuevas-Diarte, M. A.; Haget, Y.; Mondieig, D.; Kok, I. C.; Verdonk, M. L.; Van Miltenburg, J. C.; Oonk, H. A. J.

1999-03-01

The systems 2-methylnaphthalene+2-chloronaphthalene and 2-methylnaphthalene+2-bromonaphthalene belong to the exceptional group of binary systems where the formation of mixed crystals goes together with a solid-liquid phase diagram with a maximum. For these systems a thermodynamic analysis is presented which is based on new phase diagram and thermochemical data. The excess Gibbs energies, excess enthalpies, and excess entropies of the mixed crystalline state all are negative. These properties correspond to a net attraction between methyl and substituted halogen. Additional evidence of such an attraction is given by the outcome of a statistical search on intermolecular contacts, in the crystalline state of pure substances, among methyl+halogen, halogen+halogen, and methyl+methyl.

A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems

Directory of Open Access Journals (Sweden)

Christer B. Aakeröy

2015-09-01

Full Text Available As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

International Nuclear Information System (INIS)

1985-01-01

Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

Identification of the flame retardant decabromodiphenyl ethane in the environment.

Science.gov (United States)

Kierkegaard, Amelie; Björklund, Jonas; Fridén, Ulrika

2004-06-15

The brominated flame retardant decabromodiphenyl ethane, DeBDethane, is marketed as an alternative to decabromodiphenyl ether, BDE209. There are currently no data available about the presence of DeBDethane in the environment. In this study, DeBDethane was positively identified by high-resolution mass spectrometry and quantified by low-resolution mass spectrometry with electron capture negative ionization in sewage sludge, sediment, and indoor air. It was found in 25 of the 50 Swedish sewage treatment plants investigated, with estimated levels up to about 100 ng/g dry weight. The concentration of DeBDethane in sediment from Western Scheldt in The Netherlands was 24 ng/g dry weight, and in an air sample from a Swedish electronics dismantling facility it was 0.6 ng/m3. DeBDethane was also found together with nonabromodiphenyl ethanes in water piping insulation. All samples contained BDE209 in higher concentrations as compared to DeBDethane (DeBDethane/BDE209 ratios ranging from 0.02 to 0.7), probably reflecting the higher and longer usage of BDE209. There is an ongoing risk assessment within the European Union regarding BDE209. Since DeBDethane has similar applications, it is important to investigate its environmental behavior before using it to replace BDE209.

GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE (EDS) ALTERS DEVELOPMENT OF THE MOUSE TESTIS

Science.gov (United States)

GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE (EDS) ALTERS DEVELOPMENT OF THE MOUSE TESTIS. D.K. Tarka*1,2, J.D. Suarez*2, N.L. Roberts*2, J.M. Rogers*1,2, M.P. Hardy3, and G.R. Klinefelter1,2. 1University of North Carolina, Curriculum in Toxicology, Chapel Hill, NC; 2USEPA,...

Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α.

Science.gov (United States)

Winiewska, Maria; Kucińska, Katarzyna; Makowska, Małgorzata; Poznański, Jarosław; Shugar, David

2015-10-01

The interaction of human CK2α (hCK2α) with nine halogenated benzotriazoles, TBBt and its analogues representing all possible patterns of halogenation on the benzene ring of benzotriazole, was studied by biophysical methods. Thermal stability of protein-ligand complexes, monitored by calorimetric (DSC) and optical (DSF) methods, showed that the increase in the mid-point temperature for unfolding of protein-ligand complexes (i.e. potency of ligand binding to hCK2α) follow the inhibitory activities determined by biochemical assays. The dissociation constant for the ATP-hCK2α complex was estimated with the aid of microscale thermophoresis (MST) as 4.3±1.8 μM, and MST-derived dissociation constants determined for halogenated benzotriazoles, when converted according to known ATP concentrations, perfectly reconstruct IC50 values determined by the biochemical assays. Ligand-dependent quenching of tyrosine fluorescence, together with molecular modeling and DSC-derived heats of unfolding, support the hypothesis that halogenated benzotriazoles bind in at least two alternative orientations, and those that are efficient hCK2α inhibitors bind in the orientation which TBBt adopts in its complex with maize CK2α. DSC-derived apparent heat for ligand binding (ΔΔHbind) is driven by intermolecular electrostatic interactions between Lys68 and the triazole ring of the ligand, as indicated by a good correlation between ΔΔHbind and ligand pKa. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly (~40 kJ/mol), relative to possible intermolecular halogen/hydrogen bonding (less than 10 kJ/mol), in binding of halogenated benzotriazoles to the ATP-binding site of hCK2α. This article is part of a Special Issue entitled: Inhibitors of Protein Kinases. Copyright © 2015 Elsevier B.V. All rights reserved.

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

Energy Technology Data Exchange (ETDEWEB)

Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

1981-02-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

International Nuclear Information System (INIS)

Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

1981-01-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

Geological and geochemical characteristics of the secondary biogenic gas in coalbed gases, Huainan coalfield

Energy Technology Data Exchange (ETDEWEB)

Xiaojun, Zhang; Zhenglin, Cao; Mingxin, Tao; Wanchun, Wang; Jinlong, Ma

2010-09-15

The research results show that the compositions of coalbed gases in Huainan coalfield have high content methane, low content heavy hydrocarbons and carbon dioxide, and special dry gas. The evolution coal is at the stage of generation of thermogenic gases, but the d13C1 values within the range of biogenic gas (d13C1 values from -56.7{per_thousand} to -67.9{per_thousand}). The d13C2 value of coalbed gases in Huainan coalfield shows not only the features of the thermogenic ethane, but also the mixed features of the biogenic methane and thermogenic ethane. In geological characteristics, Huainan coalfield has favorable conditions of generation of secondary biogenic gas.

Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

Science.gov (United States)

Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

2017-09-01

Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

Organohalide respiration in pristine environments: implications for the natural halogen cycle.

Science.gov (United States)

Atashgahi, Siavash; Häggblom, Max M; Smidt, Hauke

2018-03-01

Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens could have primed development of metabolic machineries for their degradation, especially in microorganisms. Among these, a special group of anaerobic microorganisms was discovered that could conserve energy by reducing organohalogens as terminal electron acceptor in a process termed organohalide respiration. Originally discovered in a quest for biodegradation of anthropogenic organohalogens, these organohalide-respiring bacteria (OHRB) were soon found to reside in pristine environments, such as the deep subseafloor and Arctic tundra soil with limited/no connections to anthropogenic activities. As such, accumulating evidence suggests an important role of OHRB in local natural halogen cycles, presumably taking advantage of natural organohalogens. In this minireview, we integrate current knowledge regarding the natural origin and occurrence of industrially important organohalogens and the evolution and spread of OHRB, and describe potential implications for natural halogen and carbon cycles. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

Science.gov (United States)

Låg, M; Omichinski, J G; Dybing, E; Nelson, S D; Søderlund, E J

1994-10-01

A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane > 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated

Extending Halogen-based Medicinal Chemistry to Proteins: IODO-INSULIN AS A CASE STUDY.

Science.gov (United States)

El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B; Smith, Brian J; Menting, John G; Whittaker, Jonathan; Lawrence, Michael C; Meuwly, Markus; Weiss, Michael A

2016-12-30

Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (Tyr B26 ) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-Tyr B26 ]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (Tyr B16 , Phe B24 , Phe B25 , 3-I-Tyr B26 , and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-Tyr B26 ]insulin analog (determined as an R 6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-Tyr B26 in a receptor complex must differ from that in the free hormone. Based on the recent structure of a "micro-receptor" complex, we predict that 3-I-Tyr B26 engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such "halogen engineering" promises to extend principles of medicinal chemistry to proteins. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Chiral halogenated Schiff base compounds: green synthesis, anticancer activity and DNA-binding study

Science.gov (United States)

Ariyaeifar, Mahnaz; Amiri Rudbari, Hadi; Sahihi, Mehdi; Kazemi, Zahra; Kajani, Abolghasem Abbasi; Zali-Boeini, Hassan; Kordestani, Nazanin; Bruno, Giuseppe; Gharaghani, Sajjad

2018-06-01

Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV-vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (Rsbnd ClBr) > (Rsbnd Cl2) > (Rsbnd Br2) > (Rsbnd I2) and (Ssbnd ClBr) > (Ssbnd Cl2) > (Ssbnd Br2) > (Ssbnd I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the Ssbnd and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (Hsbnd and X-bond and hX-bond) between synthesized compounds and base pairs of DNA.

Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

International Nuclear Information System (INIS)

Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D.; DeYoung, Paul A.; Blum, Arlene; Stapleton, Heather M.; Peaslee, Graham F.

2015-01-01

A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams

Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

Energy Technology Data Exchange (ETDEWEB)

Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D. [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States); DeYoung, Paul A. [Department of Physics, Hope College, 27 Graves Place, Holland, MI 49423 (United States); Blum, Arlene [Green Science Policy Institute, Box 5455, Berkeley, CA 94705 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Duke University, LSRC Box 90328, Durham, NC 27708 (United States); Peaslee, Graham F., E-mail: peaslee@hope.edu [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)

2015-09-01

A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams.

Utilization of coalbed methane

Energy Technology Data Exchange (ETDEWEB)

Gustavson, J.B. [Gustavson Associates Inc., Boulder, CO (United States)

1996-02-01

Substantial progress has been made in capturing coalbed methane (CBM gas), which constitutes a valuable source of clean burning energy. It is of importance to study the various potential uses of coalbed methane and to understand the various technologies required, as well as their economics and any institutional constraints. In industrialised countries, the uses of coalbed methane are almost solely dependent on microeconomics; coalbed methane must compete for a market against natural gas and other energy sources - and frequently, coalbed methane is not competitive against other energy sources. In developing countries, on the other hand, particularly where other sources of energy are in short supply, coalbed methane economics yield positive results. Here, constraints to development of CBM utilization are mainly lack of technology and investment capital. Sociological aspects such as attitude and cultural habits, may also have a strong negative influence. This paper outlines the economics of coalbed methane utilization, particularly its competition with natural gas, and touches upon the many different uses to which coalbed methane may be applied. 24 refs., 4 figs.

Doses from radioactive methane

International Nuclear Information System (INIS)

Phipps, A.W.; Kendall, G.M.; Fell, T.P.; Harrison, J.D.

1990-01-01

A possible radiation hazard arises from exposure to methane labelled with either a 3 H or a 14 C nuclide. This radioactive methane could be released from a variety of sources, e.g. land burial sites containing radioactive waste. Standard assumptions adopted for vapours would not apply to an inert alkane like methane. This paper discusses mechanisms by which radioactive methane would irradiate tissues and provides estimates of doses. Data on skin thickness and metabolism of methane are discussed with reference to these mechanisms. It is found that doses are dominated by dose from the small fraction of methane which is inhaled and metabolised. This component of dose has been calculated under rather conservative assumptions. (author)

Correlation and extrapolation scheme for the compostition and temperature dependence of viscosity of binary gaseous mixtures: Carbon dioxide + ethane

International Nuclear Information System (INIS)

Hendl, S.; Vogel, E.

1995-01-01

Experimental viscosity data of ethane, carbon dioxide, and three mole fractions of the binary system carbon dioxide + ethane in the temperature range 293.15≤T≤633.15 K and in the density range 0.01≤p≤0.05 mol · L -1 reported earlier were evaluated simultaneously to find out a useful correlation and extrapolation scheme for the viscosity of binary systems in the range of moderate densities. A procedure based on the ideas of the modified Enskog theory has been found to give the best results. Dependent on temperature, the collision diameters related to the equilibrium radial distribution function at contact are fitted to viscosity values of the pure substances and of at least one mixture. The results are compared with experimental data from the literature. A recommendation is given concerning the density range in which the first density contribution to the viscosity coefficient of the system carbon dioxide + ethane is sufficient to be included

Can Halogen Enrichment in Reduced Enstatite Chondrites Provide Clues to Volatile Accretion in the Early Earth?

Science.gov (United States)

Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Ballentine, C.

2013-12-01

Understanding how the Earth obtained and ultimately retained its volatiles is important for our overall understanding of large scale planetary evolution. Numerous models exist for the heterogeneous accretion of volatiles to early Earth, but accounting for all elements through accretion of typical planetary building blocks (e.g., CI chondrites) is difficult. Proto-planetary collisions resulting in the accretion of volatile-poor material under reducing conditions followed by accretion of volatile-rich material under oxidizing conditions has been suggested in such models [e.g., 1]. The heavy halogens (Cl, Br and I), a group of moderately volatile elements, are excellent tracers of planetary processing due to their low abundance and incompatible nature. Therefore characterizing halogen abundance and distribution in materials that accreted to form the planets, e.g., primitive meteorites, is crucial. One group of primitive meteorites, the enstatite chondrites (EC's), are amongst the most reduced materials in the solar system as evidenced by their unique mineral assemblage. Yet despite forming under ultra-reducing conditions, they are enriched in the moderately volatile elements, such as the halogens. The ECs are of particular interest owing to their oxygen isotopic composition which plots along the terrestrial fractionation line, linking them isotopically to the Earth-Moon system. These samples can thus potentially provide clues on the accretion of moderately volatile element rich material under reducing conditions, such as it may have existed during the early stages of Earth's accretion. Chlorine, Br and I concentrations in ECs were determined through step-heating small neutron-irradiated samples (0.3 to 3.3 mg) and measured by mass spectrometry using the noble gas proxy isotopes 38ArCl/Cl, 80KrBr/Br and 128XeI/I. The EH chondrites are consistently enriched in the heavy halogens (up to 330 ppm Cl, 2290 ppb Br and 180 ppb I), compared to other ordinary and carbonaceous

Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

Science.gov (United States)

Crebelli, R; Carere, A; Leopardi, P; Conti, L; Fassio, F; Raiteri, F; Barone, D; Ciliutti, P; Cinelli, S; Vericat, J A

1999-03-01

Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Science.gov (United States)

Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

2012-10-03

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

[Near infrared light irradiator using halogen lamp].

Science.gov (United States)

Ide, Yasuo

2012-07-01

The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

Martian methane plume models for defining Mars rover methane source search strategies

Science.gov (United States)

Nicol, Christopher; Ellery, Alex; Lynch, Brian; Cloutis, Ed

2018-07-01

The detection of atmospheric methane on Mars implies an active methane source. This introduces the possibility of a biotic source with the implied need to determine whether the methane is indeed biotic in nature or geologically generated. There is a clear need for robotic algorithms which are capable of manoeuvring a rover through a methane plume on Mars to locate its source. We explore aspects of Mars methane plume modelling to reveal complex dynamics characterized by advection and diffusion. A statistical analysis of the plume model has been performed and compared to analyses of terrestrial plume models. Finally, we consider a robotic search strategy to find a methane plume source. We find that gradient-based techniques are ineffective, but that more sophisticated model-based search strategies are unlikely to be available in near-term rover missions.

Efficient Reservoir Simulation with Cubic Plus Association and Cross-Association Equation of State for Multicomponent Three-Phase Compressible Flow with Applications in CO2 Storage and Methane Leakage

Science.gov (United States)

Moortgat, J.

2017-12-01

We present novel simulation tools to model multiphase multicomponent flow and transport in porous media for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2 and H2S. Such mixtures often occur when CO2 is injected and stored in saline aquifers, or when methane is leaking into groundwater. To accurately predict the species transfer between aqueous, gaseous and oleic phases, and the subsequent change in phase properties, the self- and cross-associating behavior of molecules needs to be taken into account, particularly at the typical temperatures and pressures in deep formations. The Cubic-Plus-Association equation-of-state (EOS) has been demonstrated to be highly accurate for such problems but its excessive computational cost has prevented widespread use in reservoir simulators. We discuss the thermodynamical framework and develop sophisticated numerical algorithms that allow reservoir simulations with efficiencies comparable to a simple cubic EOS. This approach improves our predictive powers for highly nonlinear fluid behavior related to geological carbon sequestration, such as density driven flow and natural convection (solubility trapping), evaporation of water into the CO2-rich gas phase, and competitive dissolution-evaporation when CO2 is injected in, e.g., methane saturated aquifers. Several examples demonstrate the accuracy and robustness of this EOS framework for complex applications.

Anti-inflammatory actions of a taurine analogue, ethane β-sultam, in phagocytic cells, in vivo and in vitro.

Science.gov (United States)

Ward, Roberta J; Lallemand, Frederic; de Witte, Philippe; Crichton, Robert R; Piette, Jacques; Tipton, Keith; Hemmings, Karl; Pitard, Arnaud; Page, Mike; Della Corte, Laura; Taylor, Deanna; Dexter, David

2011-03-15

The ability of a taurine prodrug, ethane β-sultam, to reduce cellular inflammation has been investigated, in vitro, in primary cultures of alveolar macrophages and an immortilised N9 microglial cell line and in vivo in an animal model of inflammation and control rats. Ethane β-sultam showed enhanced ability to reduce the inflammatory response in alveolar macrophages, as assayed by the lipopolysaccharide-stimulated-nitric oxide release, (LPS stimulated-NO), in comparison to taurine both in vitro (10 nM, 50 nM) and in vivo (0.15 mmol/kg/day by gavage). In addition, ethane β-sultam, (50, 100 and 1000 nM) significantly reduced LPS-stimulated glutamate release from N9 microglial cells to a greater extent than taurine. The anti-inflammatory response of taurine was shown to be mediated via stabilisation of IkBα. The use of a taurine prodrug as therapeutic agents, for the treatment of neurological conditions, such as Parkinson's and Alzheimer's disease and alcoholic brain damage, where activated phagocytic cells contribute to the pathogenesis, may be of great potential. Copyright © 2011 Elsevier Inc. All rights reserved.

Genomic and Transcriptomic Analysis of Growth-Supporting Dehalogenation of Chlorinated Methanes in Methylobacterium