The reaction of fluorine atoms with methanol: yield of CH3O/CH2OH and rate constant of the reactions CH3O + CH3O and CH3O + HO2.

Science.gov (United States)

Assaf, Emmanuel; Schoemaecker, Coralie; Vereecken, Luc; Fittschen, Christa

2018-04-25

Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2. The rate constants for the reaction of both radicals with O2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO2 concentrations in the presence of different O2 concentrations. The following yields have then been determined from time-resolved HO2 profiles: φCH2OH = (0.497 ± 0.013) and φCH3O = (0.503 ± 0.013). Experiments under low O2 concentrations lead to reaction mixtures containing nearly equal amounts of HO2 (converted from the first reaction) and CH3O (from the second reaction). The subsequent HO2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH3O + CH3O) = (7.0 ± 1.4) × 10-11 cm3 s-1 and k(CH3O + HO2) = (1.1 ± 0.2) × 10-10 cm3 s-1. The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH3OH + O2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH3O + HO2) = 4.7 × 10-11 cm3 s-1 has been obtained, in good agreement with the experiment.

Infrared Spectra and Structures of SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} Intermediates Prepared in Reactions of Laser-ablated Silicon Atoms with Ethane

Energy Technology Data Exchange (ETDEWEB)

Cho, Han-Gook [Incheon National University, Incheon (Korea, Republic of); Andrews, Lester [University of Virginia, Charlottesville (United States)

2016-03-15

SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} were observed in the matrix IR spectra following reactions of laser-ablated Si atoms with ethane on the basis of correlation with computed frequencies. Evidently photon energy is required for the formation of the cyclic Si compound. These Si complexes are similar to the primary products in the previous studies of group 4 metals, in line with the previous results that s{sup 2}p{sup 2} and s{sup 2}d{sup 2} electronic configurations yield similar products. The relatively long C–C bond in the cyclic Si product reflects the structural strain, and the short C-Si and C-C bonds of CH{sub 3}CH=SiH{sub 2} and CH{sub 2}=CH-SiH{sub 3} show that they are true double bonds in line with the natural bond orders. Reactions of transition-metal atoms with small alkanes and halomethanes have been studied in a series of recent investigations. High oxidation-state products (methylidenes and methylidynes) along with insertion complexes were identified in the matrix spectra. It is interesting whether or not Si, a group 14 metalloid, undergoes similar reactions with larger hydrocarbons to provide higher oxidation-state compounds.

Atmospheric chemistry of CF3CH2CH2OH

DEFF Research Database (Denmark)

Hurley, Michael D.; Misner, Jessica A.; Ball, James C.

2005-01-01

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF3CH2C(O)H and CF3CH2CH2OH in 700 Torr of N-2 or air diluent at 296 2 K. The rate constants determined were k(Cl+CF3CH2C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF3CH2C(O)H) = (2.57 +/- 0.44...

CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4: Infrared spectra, radiative efficiencies, and global warming potentials

International Nuclear Information System (INIS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-01-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600–3500 cm"−"1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm"−"1 molecule"−"1): CH_3Cl, 660–780 cm"−"1, (3.89±0.19)×10"−"1"8; CH_2Cl_2, 650–800 cm"−"1, (2.16±0.11)×10"−"1"7; CHCl_3, 720–810 cm"−"1, (4.08±0.20)×10"−"1"7; and CCl_4, 730–825 cm"−"1, (6.30±0.31)×10"−"1"7. CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons. - Highlights: • Infrared spectra reported for CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4. • REs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1, respectively. • GWPs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 5, 8, 15, and 1775, respectively.

Ultrasonic Examination of Double-Shell Tank 241-AY-101 Examination Completed August 2003

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2003-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-AY-101. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the secondary tank. The requirements for the ultrasonic examination of Tank 241-AY-101 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning or pitting that might be present in the wall of the secondary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP--11832 (Jensen 2002) and summarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA ultrasonic examinations

Ultrasonic Examination of Double-Shell Tank 241-AP-104. Examination Completed August 2004

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2004-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-AP-104. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-AP-104 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP-17750 (Jensen 2003) and summarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA ultrasonic examinations

Ultrasonic Examination of Double-Shell Tank 241-SY-103. Examination completed February 2004

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2004-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-SY-103. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-SY-103 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP-17750 (Jensen 2003) and summarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA ultrasonic examinations

Ultrasonic Examination of Double-Shell Tank 214-AW-102 Knuckle Region. Examination completed February 2003

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2003-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic examination of the knuckle region of Double-Shell Tank 241-AW-102 utilizing the Remotely Operated Nondestructive Examination (RONDE) system. The purpose of this examination was to provide information that could be used to evaluate the integrity of the knuckle region of the primary tank. The requirements for the ultrasonic examination of Tank 241-AW-102 were to detect, characterize (identify, size, and locate), and record measurements made of any circumferentially oriented cracks that might be present in the knuckle area of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP-7869, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided t o PNNL for third-party evaluation. PNNL is responsible for preparing a report(s) that describes the results of the COGEMA ultrasonic examinations

Ultrasonic Examination of Double-Shell Tank 241-AZ-102 Examination Completed August 2003

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2003-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-AZ-102. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-AZ-102 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plat (ETP), RPP-11832 (Jensen 2002) and summarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA ultrasonic examinations

Ultrasonic Examination of Double-Shell Tank 241-SY-102. Examination Completed June 2004

International Nuclear Information System (INIS)

Pardini, Allan F.; Posakony, Gerald J.

2004-01-01

COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-SY-102. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-SY-102 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP-17750 (Jensen 2003) and/SUMmarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA

Environmental Requirements Management

Energy Technology Data Exchange (ETDEWEB)

Cusack, Laura J.; Bramson, Jeffrey E.; Archuleta, Jose A.; Frey, Jeffrey A.

2015-01-08

CH2M HILL Plateau Remediation Company (CH2M HILL) is the U.S. Department of Energy (DOE) prime contractor responsible for the environmental cleanup of the Hanford Site Central Plateau. As part of this responsibility, the CH2M HILL is faced with the task of complying with thousands of environmental requirements which originate from over 200 federal, state, and local laws and regulations, DOE Orders, waste management and effluent discharge permits, Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) response and Resource Conservation and Recovery Act (RCRA) corrective action documents, and official regulatory agency correspondence. The challenge is to manage this vast number of requirements to ensure they are appropriately and effectively integrated into CH2M HILL operations. Ensuring compliance with a large number of environmental requirements relies on an organization’s ability to identify, evaluate, communicate, and verify those requirements. To ensure that compliance is maintained, all changes need to be tracked. The CH2M HILL identified that the existing system used to manage environmental requirements was difficult to maintain and that improvements should be made to increase functionality. CH2M HILL established an environmental requirements management procedure and tools to assure that all environmental requirements are effectively and efficiently managed. Having a complete and accurate set of environmental requirements applicable to CH2M HILL operations will promote a more efficient approach to: • Communicating requirements • Planning work • Maintaining work controls • Maintaining compliance

Activation of sp3-CH Bonds in a Mono(pentamethylcyclopentadienyl)yttrium Complex. X-ray Crystal Structures and Dynamic Behavior of Cp*Y(o-C6H4CH2NMe2)2 and Cp*Y[o-C6H4CH2NMe(CH2-μ)][μ-o-C6H4CH2NMe(CH2-μ)]YCp*[THF

NARCIS (Netherlands)

Booij, Martin; Kiers, Niklaas H.; Meetsma, Auke; Teuben, Jan H.; Smeets, Wilberth J.J.; Spek, Anthony L.

1989-01-01

Reaction of Y(o-C6H4CH2NMe2)3 (1) with Cp*H gives Cp*Y(o-C6H4CH2NMe2)2 (2), which crystallizes in the monoclinic space group P21/n (No. 14) with a = 18.607 (4) Å, b = 15.633 (3) Å, c = 8.861 (3) Å, β = 102.73 (3)°, and Z = 4. Least-squares refinement with 3006 independent reflections (F > 4.0σ(F))

Synthesis and thermolysis of Cp*(C5Me4CH2)TiR complexes

NARCIS (Netherlands)

Luinstra, GA; Brinkmann, PHP; Teuben, JH; Luinstra, Gerrit A.

1997-01-01

Substitution of the chloride in Cp*FvTiCl with MR (Fv = C5Me4CH2; R = Me, CH2SiMe3, CH2CMe3, CH = CH2, M = Li; R = CH2Ph, M = K; R = C3H5, M = MgCl; R = Ph, M = Na . NaCl) gives Cp*FvTiR. NMR spectroscopic evidence points towards a series of structurally related compounds with a bent-sandwich

Thermodynamic activity of saturated solutions of CsClO4 in ethylene glycol and its analogs of the HOCH2(CH2CH2O)nCH2OH series

International Nuclear Information System (INIS)

Krasnoperova, A.P.; Ivanova, E.F.; Kijko, S.M.; Yukhno, G.D.

1997-01-01

Solubility of CsClO 4 in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with molar mass 300 and 400 in the temperature range of 273.15-318.15 K has been ascertained by the method of radioactive indicators. Dependence of saturated solutions activity on temperature, dielectric permittivity and the number of (CH 2 CH 2 O) ether groups in glycols is discussed

Crystallization and X-ray diffraction analysis of the CH domain of the cotton kinesin GhKCH2

Energy Technology Data Exchange (ETDEWEB)

Qin, Xinghua [China Agricultural University, No. 2 Yuanmingyuanxilu, Haidian District, Beijing 100094, People’s Republic of (China); The Fourth Military Medical University, No. 169 Changlexi Road, Xincheng District, Xi’an 710032, People’s Republic of (China); Chen, Ziwei; Li, Ping; Liu, Guoqin, E-mail: liu@cau.edu.cn [China Agricultural University, No. 2 Yuanmingyuanxilu, Haidian District, Beijing 100094, People’s Republic of (China)

2016-02-19

The cloning, expression, purification and crystallization of the CH domain of the plant-specific kinesin GhKCH2 is reported. GhKCH2 belongs to a group of plant-specific kinesins (KCHs) containing an actin-binding calponin homology (CH) domain in the N-terminus. Previous studies revealed that the GhKCH2 CH domain (GhKCH2-CH) had a higher affinity for F-actin (K{sub d} = 0.42 ± 0.02 µM) than most other CH-domain-containing proteins. To understand the underlying mechanism, prokaryotically expressed GhKCH2-CH (amino acids 30–166) was purified and crystallized. Crystals were grown by the sitting-drop vapour-diffusion method using 0.1 M Tris–HCl pH 7.0, 20%(w/v) PEG 8000 as a precipitant. The crystals diffracted to a resolution of 2.5 Å and belonged to space group P2{sub 1}, with unit-cell parameters a = 41.57, b = 81.92, c = 83.00 Å, α = 90.00, β = 97.31, γ = 90.00°. Four molecules were found in the asymmetric unit with a Matthews coefficient of 2.22 Å{sup 3} Da{sup −1}, corresponding to a solvent content of 44.8%.

Effects of forage types on digestibility, methane emissions, and nitrogen utilization efficiency in two genotypes of hill ewes.

Science.gov (United States)

Zhao, Y G; Annett, R; Yan, T

2017-08-01

Thirty-six nonpregnant hill ewes (18 pure Scottish Blackface and 18 Swaledale × Scottish Blackface) aged 18 mo and weighing 48 ± 4.8 kg were allocated to 3 forage treatments balanced for genotype and BW. Each genotype was offered 3 forages (pelleted ryegrass, fresh lowland grass, and fresh hill grass) ad libitum with 6 ewes for each of the 6 genotype × diet combination treatments. Pelleted ryegrass was sourced from a commercial supplier (Drygrass South Western Ltd, Burrington, UK). Fresh lowland grass was harvested daily in the morning from a third regrowth perennial ryegrass () sward. Fresh hill grass was harvested from a seminatural hill grassland every 2 d and stored in plastic bags at 4 to 5°C until offered. The animals were individually housed in pens and offered experimental diets for 14 d before being transferred to 6 individual respiration chambers for a further 4 d, during which feed intake, fecal and urine outputs, and CH emissions were measured. There was no interaction between genotype and forage types on any variable measured. In a comparison of effects of the 3 forages, pelleted ryegrass had the greatest ( reduce CH emissions per kilogram DMI. These equations add new information in predicting enteric CH emissions and N utilization efficiency and can be used to quantify the environmental footprint of hill sheep production systems.

OXIDATIVE ALKYLATION OF (ETA-5-C5ME5)2TIR (R=CL, ME, ET, CH=CH2, PH, OME, N=C(H)TERT-BU) TO (ETA-5-C5ME5)2TI(ME)R BY GROUP-12 ORGANOMETALLIC COMPOUNDS MME2

NARCIS (Netherlands)

LUINSTRA, GA; TEUBEN, JH

1991-01-01

Oxidative alkylation of Cp*2TiX (Cp*: eta-5-C5Me5; X = OMe, Cl, N = C(H)tBu) and Cp*2TiMe by CdMe2 or ZnMe2 gives diamagnetic Cp*2Ti(Me)X and Cp*2TiMe2 respectively, and cadmium or zinc. The reactions of Cp*2TiR (R = Et, CH = CH2, Ph) with MMe2 (M = Cd, Zn) give statistical mixtures of Cp*2Ti(Me)R,

Atmospheric Chemistry of CH3CH2OCH3

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Bjørn Svendsen, Sissel; Østerstrøm, Freja From

2017-01-01

The atmospheric chemistry of methyl ethyl ether, CH3CH2OCH3, was examined using FT-IR/relative-rate methods. Hydroxyl radical and chlorine atom rate coefficients of k(CH3CH2OCH3+OH) = (7.53 ± 2.86) × 10−12 cm3 molecule−1 s−1 and k(CH3CH2OCH3+Cl) = (2.35 ± 0.43) × 10−10 cm3 molecule−1 s−1 were...

Thermodynamic study of (alkyl esters+{alpha},{omega}-alkyl dihalides) V. H{sub m}{sup E}andV{sub m}{sup E} for 25 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}CH{sub 3}+(1-x){alpha},{omega}-ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl{r_brace}, where u=1 to 5, {alpha}=1 and v={omega}=2 to 6

Energy Technology Data Exchange (ETDEWEB)

Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain)]. E-mail: jortega@dip.ulpgc.es; Marrero, E. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain)

2007-05-15

The experimental data of excess molar enthalpies H{sub m}{sup E} and excess molar volumes V{sub m}{sup E} are presented for a set of 25 binary mixtures comprised of the first five methyl esters C{sub u-1}H{sub 2u-1}COOCH{sub 3} (u=1 to 5) and five {alpha},{omega}-dichloroalkanes, ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl (v=2 to 6), obtained at a temperature of 298.15K and atmospheric pressure. Except for the mixtures with u=1 and v=2 to 6, which are all endothermic and with u=5 and v=2 to 6, which are all exothermic, the others present net endo/exothermic effects and these mixing effects evolve quasiregularly, from endothermic to exothermic, depending on the dichloroalkane present. However, the V{sub m}{sup E} are positive in most mixtures except for those corresponding to u=4,5 and v=5,6, which present contraction effects. These results indicate a set of specific interactions with simultaneous effects for V{sub m}{sup E} of expansion/contraction and for exothermic/endothermic H{sub m}{sup E} for this set of mixtures. The change in V{sub m}{sup E} with the chain length of the compounds is irregular. To achieve a good application of the UNIFAC model using the version of Dang and Tassios, parameters of the ester (G)/dichloride (G') interaction were calculated again, making a distinction, during its application, dependent on the acid part of the ester u. Hence, interaction parameters are presented as a function of u, and of the dichloroalkane chain length v. The most appropriate general expression was of the type:a{sub G/G{sup '}}={phi}(u,v)={sigma}sub(i=0)sup(n)a{sub i-1}u{sup i-1}+{sigma}sub(i=0= )sup(n)b{sub i-1}v{sup i-1}and with this proposal good estimations of enthalpies were obtained with the UNIFAC model.

Thermodynamic study of (alkyl esters + {alpha},{omega}-alkyl dihalides) VII. H{sub m}{sup E} and V{sub m}{sup E} for 20 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}C{sub 3}H{sub 7} + (1 - x){alpha},{omega}-ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl{r_brace}, where u = 1 to 4, {alpha} = 1 and v = {omega} = 2 to 6. An analysis of behavior using the COSMO-RS methodology

Energy Technology Data Exchange (ETDEWEB)

Marrero, E. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain); Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain)], E-mail: jortega@dip.ulpgc.es; Palomar, J. [Seccion de Ingenieria Quimica, Dpto. de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

2009-03-15

Summary: Excess enthalpies H{sub m}{sup E} and excess volumes V{sub m}{sup E} obtained at a temperature of 298.15 K and atmospheric pressure are presented for a set of 20 binary mixtures comprised of the first four propyl esters, C{sub u-1}H{sub 2u-1}COOC{sub 3}H{sub 7} (u = 1 to 4), and five {alpha},{omega}-dichloroalkanes, ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl (v = 2 to 6). All the mixtures are exothermic except for those corresponding to propyl methanoate with v {>=} 4. The V{sub m}{sup E} are positive in most mixtures except for those where v = 4, 5, 6, for V{sub m}{sup E}<0. There is a regular rise in H{sub m}{sup E} with v, while the increase in u produces a greater exothermicity in the mixing process, which becomes inverted for propyl butanoate. The variation in V{sub m}{sup E} with the chain length of the compounds of the mixtures studied is not regular since both the enthalpic and the volumetric effects are due to interactions of different nature, positive and negative. Interpretation of the behavior was assisted by applying the quantum-chemistry method COSMO-RS. This method describes qualitatively and quantitatively the contribution of the different types of interactions, electrostatic, van der Waals, and those due to the (Cl, Cl) bond in the dihalide, and the influence of the ester and dichloroalkane chains. This information was also useful to adequately modify the application of the UNIFAC group contribution model, proposing parameters for the Cl, Cl/carboxylate interaction that vary with the chain length of the compounds involved. With this modification, the results estimated by UNIFAC model can be considered good.

Eocene age of the Baranowski Glacier Group at Red Hill, King George Island, West Antarctica

Directory of Open Access Journals (Sweden)

Mozer Anna

2015-12-01

Full Text Available Radiometric and geochemical studies were carried out at Red Hill in the southern part of King George Island (South Shetland Islands, northern Antarctic Peninsula on the Bransfield Strait coast. The rock succession at Red Hill has been determined to represent the Baranowski Glacier Group that was previously assigned a Late Cretaceous age. Two formations were distinguished within this succession: the lower Llano Point Formation and the upper Zamek Formation. These formations have stratotypes defined further to the north on the western coast of Admiralty Bay. On Red Hill the Llano Point Formation consists of terrestrial lavas and pyroclastic breccia; the Zamek Formation consist predominantly of fine to coarse tuff, pyroclastic breccia, lavas, tuffaceous mud-, silt-, and sandstone, locally conglomeratic. The lower part of the Zamek Formation contains plant detritus (Nothofagus, dicotyledonous, thermophilous ferns and numerous coal seams (vitrinitic composition that confirm the abundance of vegetation on stratovolcanic slopes and surrounding lowlands at that time. Selected basic to intermediate igneous rocks from the succession have been analysed for the whole-rock K-Ar age determination. The obtained results indicate that the Red Hill succession was formed in two stages: (1 from about 51–50 Ma; and (2 46–42 Ma, i.e. during the Early to Middle Eocene. This, in combination with other data obtained from other Baranowski Glacier Group exposures on western coast of Admiralty Bay, confirms the recently defined position of the volcano-clastic succession in the stratigraphic scheme of King George Island. The new stratigraphic position and lithofacies development of the Red Hill succession strongly suggest its correlation with other Eocene formations containing fossil plants and coal seams that commonly occur on King George Island.

Comparison of the reactivity of 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} with MCl{sub 4} (M=Th, U). Isolation of a thorium aryl complex or a uranium benzyne complex

Energy Technology Data Exchange (ETDEWEB)

Seaman, Lani A.; Pedrick, Elizabeth A.; Wu, Guang; Hayton, Trevor W. [California Univ., Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry; Tsuchiya, Takashi; Jakubikova, Elena [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry

2013-09-27

Individualism under actinoids: The reaction of 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} with [MCl{sub 4} (dme) {sub n}] (M=Th, n=2; M=U, n=0) gives the thorium aryl complex [Th(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 4}] or the uranium benzene complex Li[U(2,3-C{sub 6}H{sub 3}CH{sub 2}NMe{sub 2})(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 3}]. A DFT analysis suggests that the formation of a benzyne complex with uranium but not with thorium is a kinetic and not thermodynamic effect. [German] Individualismus unter Actinoiden: Die Reaktion von 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} mit [MCl{sub 4} (dme) {sub n}] (M=Th, n=2; M=U, n=0) ergibt den Thoriumarylkomplex [Th(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 4}] bzw. den Uranbenz-inkomplex Li[U(2,3-C{sub 6}H{sub 3}CH{sub 2}NMe{sub 2})(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 3}]. Einer dichtefunktionaltheoretischen Analyse zufolge ist es kinetisch und nicht thermodynamisch bedingt, dass der Benz-inkomplex im Fall von Uran entsteht, nicht aber im Fall von Thorium.

Enthalpies of solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in different H-bonding solvents: Methanol, chloroform, and water. Group contribution method as applied to the polar oligomers

Energy Technology Data Exchange (ETDEWEB)

Barannikov, Vladimir P., E-mail: vpb@isc-ras.ru [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation); Guseynov, Sabir S.; Vyugin, Anatoliy I. [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation)

2011-12-15

Highlights: > Solvation enthalpy is found for ethylene oxide oligomers in chloroform and methanol. > Coefficients of solute-solute interaction are determined for oligomers in methanol. > Enthalpies of hydrogen bonding of oligomers with chloroform and water are estimated. > Additivity scheme is developed for describing enthalpies of solvation of oligomers. - Abstract: The enthalpies of solution and solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute-solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute-solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ . mol{sup -1}. The values of group contributions and corrections are strongly influenced by solvent properties.

Characterization of Vadose Zone Sediment: Borehole 299-W23-19[SX -115] in the S-SX Waste Management Area

International Nuclear Information System (INIS)

Serne, R. Jeffrey; Schaef, Herbert T.; Bjornstad, Bruce N.; Lanigan, David C.; Gee, Glendon W.; Lindenmeier, Clark W.; Clayton, Ray E.; Legore, Virginia L.; Orr, Robert D.; O'Hara, Matthew J.; Brown, Christopher F.; Last, George V.; Kutnyakov, Igor V.; Burke, Deborah Sd; Wilson, Teresa C.; Williams, Bruce A.

2001-01-01

The Tank Farm Vadose Zone Project is led by CH2M HILL Hanford Group, Inc. Their goals include defining risks from past and future single-shell tank farm activities, identifying and evaluating the efficacy of interim measures, and collecting geo-technical information and data. The purpose of these activities is to support future decisions made by the U.S. Department of Energy regarding near-term operations, future waste retrieval, and final closure activities for the single-shell tank Waste Management Areas. To help in this effort, CH2M HILL contracted with scientists at Pacific Northwest National Laboratory to analyze sediment samples collected from borehole 299-W23-19. The conclusions reached from this study support specific mechanisms influencing subsurface migration of contaminants. The mechanisms are supported by the distributions of contaminants beneath tank farms. These observations will help DOE and CH2M HILL identify and implement viable remediation and closure activities

Dentritic Carbosilanes Containing Silicon-Bonded 1-[C6H2(CH2NMe2)2-3,5-Li-4] or 1-[C6H3(CH2NMe2)-4-Li-3] Mono-and Bis(amino)aryllithium End Groups: Structure of {[CH2SiMe2C6H3(CH2NMe2)-4-Li-3]2}2

NARCIS (Netherlands)

Koten, G. van; Kleij, A.W.; Kleijn, H.; Jastrzebski, J.T.B.H.; Smeets, W.J.J.; Spek, A.L.

1999-01-01

A useful synthetic procedure for the incorporation of the potentially multidentate monoanionic 1-[C6H2(CH2NMe2)2-3,5]- (=NCN) and 1-[C6H3(CH2NMe2)-4]- (=CN) ligands via the para-position on the periphery of carbosilane (CS) dendrimers has been developed. Lithiation of suitable brominated precursors

The assessment of the extent of the recovery of hand sensorimotor functions in the group of rehabilitated patients after stroke in the post-acute stage [Hodnocení míry úpravy senzomotorických funkcí ruky u skupiny rehabilitovaných pacientů po CMP v postakutním stádiu

Directory of Open Access Journals (Sweden)

Hana Sochorová

2010-03-01

of patients, but the results are not consistent. Some of the patients got worse and sometimes there was only a slight change. The results of an experimental group of patients must be proven by a therapy specifically targeted to influence the somatosensory functions.[VÝCHODISKA: Deficit senzomotorických funkcí ruky u pacientů po CMP je velmi častý. Přesto je algoritmus jejich obnovy relativně málo známý. Není jasné, zda rozsah či typ poruchy somatosenzorických funkcí koreluje s horší obnovou motoriky. CÍLE: Tato studie byla zaměřena na sledování senzomotorických funkcí ruky u skupiny pacientů v postakutním stádiu po ischemické CMP, lokalizované v povodí arteria cerebri media. Cílem bylo zjistit míru úpravy somatosenzorických a motorických funkcí ruky u sledované skupiny. Jedná se o první etapu výzkumu, na kterou bude navazovat sledování experimentální skupiny s terapií cílenou na somatosenzorické funkce. METODIKA: Sledovaná skupina pacientů byla léčena na oddělení kliniky lůžkové rehabilitace a prošla standardní terapií po dobu 3–4 týdnů. K hodnocení senzomotorických funkcí ruky byly použity 2 testy čití: FMT – Test srovnávání textury látek a RASP – Rivermeadské hodnocení somatosenzorických funkcí a 2 testy motoriky: NHPT – Devítikolíkový test a TMF – Test manipulačních funkcí ruky pomocí stavebnice Ministav. Testy byly provedeny na začátku a na konci terapie. VÝSLEDKY: U sledované skupiny pacientů jsme zjistili poruchy somatosenzorických funkcí a motoriky i na horní končetině nepostižené strany. Jemná motorika je přitom postižena více než somatosenzorické funkce. Největší defi cit u motorických funkcí vykazovaly úkoly vyžadující precizní úchop. Nejvýraznější změny při hodnocení pacientů byly registrovány v ADL, hodnocených indexem Barthelové – k úpravě funkcí do normy došlo u 1/3 pacientů. ZÁVĚRY: Po aplikaci standardn

Extraterrestrial Amino Acids Identified in Metal-Rich CH and CB Carbonaceous Chondrites from Antarctica

Science.gov (United States)

Burton, Aaron S.; Elsila, Jamie E.; Hein, Jason E.; Glavin, Daniel P.; Dworkin, Jason P.

2013-01-01

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondritesbut are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal-rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment(PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675(CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time-of-flight mass spectrometry and fluorescence, and gas chromatography isotope ratiomass spectrometry. The (delta D, delta C-13, delta N-15) ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (1316 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.22 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of beta-, gamma-, and delta-amino acids compared to the corresponding alpha-amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO_2(CH_3SO_3)_2, UO_2(CH_3SO_3)_2, ReO_3(CH_3SO_3), VO(CH_3SO_3)_2, and V_2O_3(CH_3SO_3)_4 and their thermal decomposition under N_2 and O_2 atmosphere

International Nuclear Information System (INIS)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S.

2011-01-01

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO_3, UO_2(CH_3COO)_2.2 H_2O, Re_2O_7(H_2O)_2, and V_2O_5 with CH_3SO_3H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO_2(CH_3SO_3)_2 (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm"3, Z=8) contains [MoO_2] moieties connected by [CH_3SO_3] ions to form layers parallel to (100). UO_2(CH_3SO_3)_2 (P2_1/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) "c"i"r"c"l"e, V=1.8937(3) nm"3, Z=8) consists of linear UO_2"2"+ ions coordinated by five [CH_3SO_3] ions, forming a layer structure. VO(CH_3SO_3)_2 (P2_1/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) "c"i"r"c"l"e, V=0.8290(2) nm"3, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO_3(CH_3SO_3) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) "c"i"r"c"l"e, V=1.1523(4) nm"3, Z=8) a chain structure exhibiting infinite O-[ReO_2]-O-[ReO_2]-O chains is formed. Each [ReO_2]-O-[ReO_2] unit is coordinated by two bidentate [CH_3SO_3] ions. V_2O_3(CH_3SO_3)_4 (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm"3, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH_3SO_3] ligands. Additional methanesulfonate ions connect the [V_2O_3] groups along [001]. Thermal decomposition of the compounds was monitored under N_2 and O_2 atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N_2 the decomposition proceeds with reduction of the metal leading to the oxides MoO_2, U_3O_7, V_4O_7, and VO_2; for MoO_2(CH_3SO_3)_2, a small amount of MoS_2 is formed. If the thermal decomposition is carried out in a atmosphere of O_2 the oxides MoO_3 and V_2O_5 are formed. (Copyright copyright 2011 WILEY-VCH Verlag

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

Late metal carbene complexes generated by multiple C-H activations: examining the continuum of M=C bond reactivity.

Science.gov (United States)

Whited, Matthew T; Grubbs, Robert H

2009-10-20

Unactivated C(sp(3))-H bonds are ubiquitous in organic chemicals and hydrocarbon feedstocks. However, these resources remain largely untapped, and the development of efficient homogeneous methods for hydrocarbon functionalization by C-H activation is an attractive and unresolved challenge for synthetic chemists. Transition-metal catalysis offers an attractive possible means for achieving selective, catalytic C-H functionalization given the thermodynamically favorable nature of many desirable partial oxidation schemes and the propensity of transition-metal complexes to cleave C-H bonds. Selective C-H activation, typically by a single cleavage event to produce M-C(sp(3)) products, is possible through myriad reported transition-metal species. In contrast, several recent reports have shown that late transition metals may react with certain substrates to perform multiple C-H activations, generating M=C(sp(2)) complexes for further elaboration. In light of the rich reactivity of metal-bound carbenes, such a route could open a new manifold of reactivity for catalytic C-H functionalization, and we have targeted this strategy in our studies. In this Account, we highlight several early examples of late transition-metal complexes that have been shown to generate metal-bound carbenes by multiple C-H activations and briefly examine factors leading to the selective generation of metal carbenes through this route. Using these reports as a backdrop, we focus on the double C-H activation of ethers and amines at iridium complexes supported by Ozerov's amidophosphine PNP ligand (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)), allowing isolation of unusual square-planar iridium(I) carbenes. These species exhibit reactivity that is distinct from the archetypal Fischer and Schrock designations. We present experimental and theoretical studies showing that, like the classical square-planar iridium(I) organometallics, these complexes are best described as nucleophilic at iridium. We discuss

Fluxes of CH4 and N2O in aspen stands grown under ambient and twice-ambient CO2

DEFF Research Database (Denmark)

Ambus, P.; Robertson, G.P.

1999-01-01

Elevated atmospheric CO2 has the potential to change below-ground nutrient cycling and thereby alter the soil-atmosphere exchange of biogenic trace gases. We measured fluxes of CH4 and N2O in trembling aspen (Populus tremuloides Michx.) stands grown in open-top chambers under ambient and twice......-ambient CO2 concentrations crossed with `high' and low soil-N conditions. Flux measurements with small static chambers indicated net CH4 oxidation in the open-top chambers. Across dates, CH4 oxidation activity was significantly (P CO2 (8.7 mu g CH4-C m(-2) h(-1)) than...... with elevated CO2 (6.5 mu g CH4-C m(-2) h(-1)) in the low N soil. Likewise, across dates and soil N treatments CH4 was oxidized more rapidly (P CO2 (9.5 mu g CH4-C m(-2) h(-1)) than in chambers with elevated CO2 (8.8 mu g CH4-C m(-2) h(-1)). Methane oxidation in soils incubated...

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

Science.gov (United States)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Hanford Tanks 241-C-202 and 241-C-203 Residual Waste Contaminant Release Models and Supporting Data

Energy Technology Data Exchange (ETDEWEB)

Deutsch, William J.; Krupka, Kenneth M.; Lindberg, Michael J.; Cantrell, Kirk J.; Brown, Christopher F.; Mattigod, Shas V.; Schaef, Herbert T.; Arey, Bruce W.

2007-09-13

As directed by Congress, the U. S. Department of Energy (DOE) established the Office of River Protection in 1998 to manage DOE's largest, most complex environmental cleanup project – retrieval of radioactive waste from Hanford tanks for treatment and eventual disposal. Sixty percent by volume of the nation's high-level radioactive waste is stored at Hanford in aging deteriorating tanks. If not cleaned up, this waste is a threat to the Columbia River and the Pacific Northwest. CH2M Hill Hanford Group, Inc., is the Office of River Protection's prime contractor responsible for the storage, retrieval, and disposal of Hanford's tank waste. As part of this effort, CH2M HILL Hanford Group, Inc. contracted with Pacific Northwest National Laboratory (PNNL) to develop release models for key contaminants that are present in residual sludge remaining after closure of Hanford Tanks 241-C-203 (C-203) and 241-C-204 (C-204). The release models were developed from data generated by laboratory characterization and testing of samples from these two tanks. These release models are being developed to support the tank closure risk assessments performed by CH2M HILL Hanford Group, Inc., for DOE.

Capture and dissociation in the complex-forming CH + H2 → CH2 + H, CH + H2 reactions.

Science.gov (United States)

González, Miguel; Saracibar, Amaia; Garcia, Ernesto

2011-02-28

The rate coefficients for the capture process CH + H(2)→ CH(3) and the reactions CH + H(2)→ CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems.

Newtonian and pseudo-Newtonian Hill problem

International Nuclear Information System (INIS)

Steklain, A.F.; Letelier, P.S.

2006-01-01

A pseudo-Newtonian Hill problem based on the Paczynski-Wiita pseudo-Newtonian potential that reproduces general relativistic effects is presented and compared with the usual Newtonian Hill problem. Poincare maps, Lyapunov exponents and fractal escape techniques are employed to study bounded and unbounded orbits. In particular we consider the systems composed by Sun, Earth and Moon and composed by the Milky Way, the M2 cluster and a star. We find that some pseudo-Newtonian systems-including the M2 system-are more stable than their Newtonian equivalent

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

Science.gov (United States)

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

Science.gov (United States)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

Science.gov (United States)

Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

2018-04-01

The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

International Nuclear Information System (INIS)

Tan, Yee Seng; Halim, Siti Nadiah Abdul; Tiekink, Edward R.T.; Sunway Univ., Bandar Sunway

2016-01-01

Crystallization of Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 from ethanol yields the coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 }.EtOH] ∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ 2 κ 2 -tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ 2 κ 2 -tridentate as for 1 but the other two being κ 2 -chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 3 .MeCN] ∞ and binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2H 2 O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 :2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH 2 (CH 2 CH 2 OH)] 4 [SO 4 ] 2 {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (4) and the salt [iPrNH 2 (CH 2 CH 2 OH)]{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 3 } (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

Replacement of CH4 in the hydrate by use of liquid CO2

International Nuclear Information System (INIS)

Ota, Masaki; Morohashi, Kenji; Abe, Yuki; Watanabe, Masaru; Smith, Richard Lee Jr.; Inomata, Hiroshi

2005-01-01

The dynamics of CH 4 replacement in the CH 4 hydrate with saturated liquid CO 2 at 273.2 K was measured with a high pressure optical cell. The results showed that CH 4 in the hydrate gradually moved to the liquid CO 2 phase while CO 2 in the liquid phase penetrated into the hydrate from the quantitative analysis. The decomposing process of the CH 4 hydrate during the replacement was analyzed with in situ Raman spectroscopy, which allowed us to distinguish the cage structure of the CH 4 hydrate and discuss the microscopic view of the replacement in the hydrate. It was found that the decomposition of the medium cage (M-cage) in the CH 4 hydrate proceeded faster than that of the small cage (S-cage). The observed rate difference could be related to the stability of the S-cage in the CH 4 hydrate or the re-formation tendency of CH 4 and water molecules in the S-cage after decomposing the hydrate structure, whereas the guest molecule exchange of CH 4 with CO 2 could occur in the M-cage. Based on the experimental data, we developed a kinetic model for calculation of the CH 4 remaining in the hydrate considering the decomposition rate difference between the M-cage and S-cage in the CH 4 hydrate. The results indicate that the driving force could be the fugacity difference between the fluid phase and the hydrate phase for the replacement process

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

Ultrasonic Examination of Double-Shell Tank 241-AY-101. Examination completed October 2007

International Nuclear Information System (INIS)

Pardini, Allan F.; Weier, Dennis R.

2008-01-01

AREVA NC Inc., under contract from CH2M Hill Hanford Group, has performed an ultrasonic examination of selected portions of Double-Shell Tank 241-AY-101. PNNL is responsible for preparing a report(s) that describes the results of the AREVA ultrasonic examinations. This report is Revision 1 - more data has been added to the original report. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-AY-101 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan, RPP-Plan-27202 (Jensen 2005) and summarized on page 1 of this document, are to be reported to CH2M Hill Hanford Group and the Pacific Northwest National Laboratory for further evaluation. Under the contract with CH2M Hill Hanford Group, all data is to be recorded on electronic media and paper copies of all measurements are provided to Pacific Northwest National Laboratory for third-party evaluation. Pacific Northwest National Laboratory is responsible for preparing a report(s) that describes the results of the AREVA NC Inc. ultrasonic examinations.

Theoretical Characteristics of Metalloporphyrins (OEP) M (CH 3 ) (M=Al, Ga, In and Tl)

OpenAIRE

Lepetit , M.B.; Kabbaj , O.K.; Zrineh , A.

2017-01-01

International audience; A theoretical study of metalloporphyrins molecules (OEP) M (CH 3) (M=Al, Ga, In and Tl) are brought to a few experimental data and to give background for future development of these complexes. The Quantum Chemistry Program (ORCA) program package based on Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TDDFT) for transitions at the B3LYP level with ANO 2ζ+P base was used for calculations and determination of structural properties, electroni...

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

Science.gov (United States)

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

Electron pairing analysis of the Fischer-type chromium-carbene complexes (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH )

Energy Technology Data Exchange (ETDEWEB)

Poater, Jordi; Cases, Montserrat; Fradera, Xavier; Duran, Miquel; Sola, Miquel

2003-10-15

The electron-pair density distributions of a series of 25 Fischer carbene complexes of the type (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH) are analyzed using the Atoms in Molecules theory. Localization and delocalization indices are used to characterize the electron pairing taking place in the Cr=C---X moiety in these complexes. Electron delocalization between the Cr and C atoms and between the C atom and the X group are related to the {pi}-donor strength of the X group and the degree of back-donation between the chromium pentacarbonyl and the carbene fragments. The results obtained with the Atoms in Molecules theory complement those obtained in a previous study by means of energy and charge decomposition analyses. Electron delocalization between the Cr atom and the X group is consistent with the hypothesis of a weak 3-center 4-electron bonding interaction in the Cr=C-X group of atoms. Except for X=H, {delta}(Cr,X) increases with the decrease of the {pi}-donor character of the X group.

A detailed study of $(n_{ch}) vs E^{had}$ and $m_{1,2}$ at different $\\sqrt{s}_{pp}$ in (pp) interactions

CERN Document Server

Basile, M; Cesare, P D; Cifarelli, L; Contin, A; Curatolo, M; D'Ali, G; Esposito, B; Giusti, P; Massam, Thomas; Nania, R; Palmonari, F; Petrosino, A; Romeo, G C; Rossi, V; Sartorelli, G; Spinetti, M; Susinno, G; Valenti, G; Votano, L; Zichichi, A

1982-01-01

By using (pp) interactions at three different CM energies, ( \\sqrt{s})/sub pp/=30, 44, 62 GeV, it is shown that the average charged- particle multiplicity (n/sub ch/) vs. the invariant mass of the hadronic system m/sub 1,2/ has the same behaviour as it has vs. 2E/sup had/. Moreover, in both cases (n/sub ch/) is shown to be nearly independent of ( \\sqrt{s})/sub pp/ and in good agreement with the average charged-particle multiplicity measured in the (e^{+}e/sup - /) annihilation.

Theoretical studies of one- and two-photon absorption properties for three molecules with different centers (B and N) and peripheral substituted groups [N(CH{sub 3}){sub 2} and CN

Energy Technology Data Exchange (ETDEWEB)

Han Deming [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); Feng Jikang, E-mail: jikangf@yahoo.co [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); College of Chemistry, Jilin University, Changchun 130023 (China); Ren Aimin [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); Shang Xiaohong [College of Chemistry, Jilin University, Changchun 130023 (China); Liu Xiaojuan [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

2009-08-15

Three molecules with different centers (boron and nitrogen) and peripheral substituted groups [N(CH{sub 3}){sub 2} and CN] have been theoretically studied with B3LYP/6-31G(d) associated with ZINDO and sum-over-states methods. The maximum two-photon absorption cross-section delta{sub max} of the molecule with boron (B) center and N(CH{sub 3}){sub 2} peripheral group is larger than that of the molecule with nitrogen (N) center and N(CH{sub 3}){sub 2} peripheral group. As for the two molecules with N center, the delta{sub max} is obviously increased with the change from N(CH{sub 3}){sub 2} to CN group. This indicates that the large intramolecular charge transfer is in favor of the TPA response.

Dočasná symetrie zdravých a protetických končetin během chůze osoby s transtibiální amputací s různým protetickým zařazením Temporal symmetry of sound and prosthetic limbs during transtibial amputee gait with various prosthetic alignment

Directory of Open Access Journals (Sweden)

Miroslav Janura

2007-01-01

Full Text Available Termín "chůze" označuje základní pohyb, jehož pomocí se jednotlivec pohybuje z jednoho místa na druhé. U osob s postižením dolních končetin je tato aktivita částečně či zcela redukována. Během biomechanického šetření chůze u osob s různým postižením se také zkoumala symetrie zatížení dolních končetin. Určité množství biomechanických studií se zaměřuje na kinematické a dynamické proměnné cyklu chůze u osob s transtibiální amputací (Bateni & Olney, 2002; Thomas et al., 2000; Perry, 2004. Zajímavým problémem je hodnocení symetrie chůze mezi osobami s transtibiální amputací a skupinami zdravých jedinců (Winter & Sienko, 1988; Dingwell, Davis, & Frazier, 1996. Miff et al. (2005 srovnává dočasnou symetrii u zdravé skupiny s hodnotami u skupiny osob s transtibiální amputací během počáteční a konečné fáze chůze. Nolan et al. (2003 se zajímal o změny v symetrii chůze ovlivněné rychlostí chůze u osob s transtibiální a transfemorální amputací ve srovnání se zdravou skupinou. Symetrii chůze u osob s transtibiální amputací, které na počátku rehabilitace nosily dvě různé protetické nohy, zkoumal Marinakis (2004. Úplná symetrie chůze není vždy žádoucí. Lidský systém s velkou strukturální asymetrií v neuromuskulární kosterní soustavě (jedna končetina byla amputována nemůže optimálně fungovat, když je chůze symetrická (Winter & Sienko, 1988. V tomto případě je lepší nesymetrická chůze s omezením reziduálního systému a mechaniky protézy. U osob, které podstoupily amputaci, může asymetrická chůze být nástrojem, jenž chrání pahýl postižené nohy. Lze říci, že asymetrie chůze je relevantním měřítkem pro zkoumání charakteristiky chůze osob s amputací a stanovení jejich sklonu k budoucí společné bolesti a degeneraci (Nolan et al., 2003. Pro chůzi osob s amputací je velmi důležitý výběr vhodn

Field measurements and modeling to resolve m2 to km2 CH4 emissions for a complex urban source: An Indiana landfill study

Directory of Open Access Journals (Sweden)

Maria Obiminda L. Cambaliza

2017-07-01

Full Text Available Large spatial and temporal uncertainties for landfill CH4 emissions remain unresolved by short-term field campaigns and historic greenhouse gas (GHG inventory models. Using four field methods (aircraft-based mass balance, tracer correlation, vertical radial plume mapping, static chambers and a new field-validated process-based model (California Landfill Methane Inventory Model, CALMIM 5.4, we investigated the total CH4 emissions from a central Indiana landfill as well as the partitioned emissions inclusive of methanotrophic oxidation for the various cover soils at the site. We observed close agreement between whole site emissions derived from the tracer correlation (8 to 13 mol s–1 and the aircraft mass balance approaches (7 and 17 mol s–1 that were statistically indistinguishable from the modeling result (12 ± 2 mol s–1 inclusive of oxidation. Our model calculations indicated that approximately 90% of the annual average CH4 emissions (11 ± 1 mol s–1; 2200 ± 250 g m–2 d–1 derived from the small daily operational area. Characterized by a thin overnight soil cover directly overlying a thick sequence of older methanogenic waste without biogas recovery, this area constitutes only 2% of the 0.7 km2 total waste footprint area. Because this Indiana landfill is an upwind source for Indianapolis, USA, the resolution of m2 to km2 scale emissions at various temporal scales contributes to improved regional inventories relevant for addressing GHG mitigation strategies. Finally, our comparison of measured to reported CH4 emissions under the US EPA National GHG Reporting program suggests the need to revisit the current IPCC (2006 GHG inventory methodology based on CH4 generation modeling. The reasonable prediction of emissions at individual U.S. landfills requires incorporation of both cover-specific landfill climate modeling (e.g., soil temperature/moisture variability over a typical annual cycle driving CH4 transport and oxidation rates as

Reactivity of the biphasic trichloroacetonitrile-CH2Cl2/H2O2 system in the epoxidation of soybean oil

Directory of Open Access Journals (Sweden)

Martinelli, Márcia

2002-06-01

Full Text Available In this work we report on the epoxidation of soybean oil by the trichloroacetonitrile -CH2Cl2/H2O2 byphasic system. The reaction was carried out at room temperature and, most importantly, in non acid conditions which prevent the opening of the oxirane ring. The epoxidized soybean oil was characterized by infrared, 1H and 13C NMR. A maximum conversion of 81 % was achieved in two hours with 86% of selectivity in epoxy groupsEn el presente trabajo informamos sobre la epoxidación de aceite de soja mediante el sistema bifásico tricloroacetonitrilo-CH2Cl2/H2O2. La reacción fue realizada bajo condiciones de temperatura ambiente y, lo más importante, en condición no ácida, lo que evita la apertura del anillo oxirano. El aceite de soja fue caracterizado por infrarrojo y RMN de 1H and 13C. En dos horas se alcanzó una conversión máxima del 81 % obteniéndose una selectividad del 86 % en grupos epóxidos

Effects of Boreal Lake Wetlands on Atmospheric 13CH3D and 12CH2D2

Science.gov (United States)

Haghnegahdar, M. A.; Kohl, I. E.; Schauble, E. A.; Walter Anthony, K. M.; Young, E. D.

2017-12-01

Recently, we developed a theoretical model to investigate the potential use of 13CH3D and 12CH2D2 as tools for tracking atmospheric methane budget. We used electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of CH4 in air (reactions with •OH and Cl•), and literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. Here we present new methane rare isotopologue data from boreal wetlands, comprising one of the most important sources, in order to evaluate the robustness of the model. Boreal wetlands (>55° N) account for more than half of the wetland area in the Northern hemisphere. We analyzed methane samples from high latitude lakes representing different geographical regions, geological and ecological contexts, methane fluxes, and isotopic signatures. Using clumped isotopes of CH4 we are able to determine the likely production mechanism for natural CH4 samples. So far, all of our analyzed samples except one plot in the microbial pure-culture methanogenesis field (Young et al. 2017) with ranges of -0.2‰ to +1.2‰ for Δ13CH3D, and -29.6‰ to -18.2‰ for Δ12CH2D2. These compositions are far from equilibrium. The one exception, from Lake Doughnut, Alaska, exhibits Δ13CH3D and Δ12CH2D2 values of +5.2‰ and +18.7‰, respectively, which fall near ambient thermodynamic equilibrium values. This may be an effect of methanotrophy. Mean Δ13CH3D and Δ12CH2D2 for all lake samples are +1.7‰ and -15.4‰ respectively, compared to our original estimate of +6.1‰ and +21.2‰ for the wetland methane source based on an assumption of equilibrium. If we assume that these samples are representative of the overall wetland source, Δ13CH3D decreases by 0.8‰ and Δ12CH2D2 decreases by 0.6‰ in our model of bulk atmospheric methane. Δ13CH3D and Δ12CH2D2 values of air (including •OH and Cl• sink

Crystal and electronic structure of (N-CH3-2,2'-bipyridinium)(dodecahydro-dicarba-nido-undecaborate)

International Nuclear Information System (INIS)

Il'inchik, E.A.; Polyanskaya, T.M.; Volkov, V.V.

2007-01-01

The compound (N-CH 3 -2,2'-bipyridinium)(dodecahydro-dicarba-nido-undecaborate) is synthesized, and its structure is determined. The compound is characterized by IR, 11 B, 14 N NMR and X-ray photoelectron spectroscopy methods. Crystallographic data are: C 13 H 23 B 9 N 2 , M=304.62, monoclinic lattice, space group P2 1 /c, a=11.840(4), b=10.051(3), c=15.573(6) A, β=102.43(3) Deg, V=1809.8(10) A 3 , Z=4, d cal =1.118 g/cm 3 , R=0.0607 [ru

Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

International Nuclear Information System (INIS)

Bachhuber, Frederik; Krach, Alexander; Furtner, Andrea; Söhnel, Tilo; Peter, Philipp; Rothballer, Jan; Weihrich, Richard

2015-01-01

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT 2 and MCh 2 boundary phases are taken into account as well as ternary M 3 T 2 Ch 2 and M 2 T 3 Ch 3 systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs 2 type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS 2 ). - Highlights: • Study of compositional stability of MTCh vs. M 3 T 2 Ch 2 and M 2 T 3 Ch 3 compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS 2

Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) VII. HmE and VmE for 20 binary mixtures {xCu-1H2u-1CO2C3H7 + (1 - x)α,ω-ClCH2(CH2)v-2CH2Cl}, where u = 1 to 4, α = 1 and v = ω = 2 to 6. An analysis of behavior using the COSMO-RS methodology

International Nuclear Information System (INIS)

Marrero, E.; Ortega, J.; Palomar, J.

2009-01-01

Summary: Excess enthalpies H m E and excess volumes V m E obtained at a temperature of 298.15 K and atmospheric pressure are presented for a set of 20 binary mixtures comprised of the first four propyl esters, C u-1 H 2u-1 COOC 3 H 7 (u = 1 to 4), and five α,ω-dichloroalkanes, ClCH 2 (CH 2 ) v-2 CH 2 Cl (v = 2 to 6). All the mixtures are exothermic except for those corresponding to propyl methanoate with v ≥ 4. The V m E are positive in most mixtures except for those where v = 4, 5, 6, for V m E m E with v, while the increase in u produces a greater exothermicity in the mixing process, which becomes inverted for propyl butanoate. The variation in V m E with the chain length of the compounds of the mixtures studied is not regular since both the enthalpic and the volumetric effects are due to interactions of different nature, positive and negative. Interpretation of the behavior was assisted by applying the quantum-chemistry method COSMO-RS. This method describes qualitatively and quantitatively the contribution of the different types of interactions, electrostatic, van der Waals, and those due to the (Cl, Cl) bond in the dihalide, and the influence of the ester and dichloroalkane chains. This information was also useful to adequately modify the application of the UNIFAC group contribution model, proposing parameters for the Cl, Cl/carboxylate interaction that vary with the chain length of the compounds involved. With this modification, the results estimated by UNIFAC model can be considered good

[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI as Cocatalyst for Coupling-Cyclization of 2-Iodophenol with Terminal Alkynes in Water

Directory of Open Access Journals (Sweden)

Panli Jiang

2018-03-01

Full Text Available A new and efficient [(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI-co-catalyzed coupling-cyclization reactions of 2-iodophenol with terminal alkynes is described. Different 2-substitued benzo[b]furan derivatives are obtained in good to excellent yields. This protocol employs a relatively low palladium(II catalyst loading in water under air conditions.

Pure- and Mixed-Gas Permeation Properties of Highly Selective and Plasticization Resistant Hydroxyl-Diamine-Based 6FDA Polyimides for CO2/CH4 Separation

KAUST Repository

Alaslai, Nasser Y.

2016-01-05

The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m2g−1) and of 6FDA-DAR (45 m2g−1) were ~18% and 32% lower than that of 6FDA-mPDA (66 m2g−1). 6FDA-mPDA had a pure-gas CO2 permeability of 14 Barrer and CO2/CH4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO2/CH4 selectivities of 92 and 94 with moderate CO2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO2/CH4 selectivity (~ 75 at CO2 partial pressure of 10 atm) due to CO2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

Pure- and Mixed-Gas Permeation Properties of Highly Selective and Plasticization Resistant Hydroxyl-Diamine-Based 6FDA Polyimides for CO2/CH4 Separation

KAUST Repository

Alaslai, Nasser Y.; Ghanem, Bader; Alghunaimi, Fahd; Litwiller, Eric; Pinnau, Ingo

2016-01-01

The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m2g−1) and of 6FDA-DAR (45 m2g−1) were ~18% and 32% lower than that of 6FDA-mPDA (66 m2g−1). 6FDA-mPDA had a pure-gas CO2 permeability of 14 Barrer and CO2/CH4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO2/CH4 selectivities of 92 and 94 with moderate CO2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO2/CH4 selectivity (~ 75 at CO2 partial pressure of 10 atm) due to CO2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

Lithostratigraphy of the Calico Hills Formation and Prow Pass Tuff (Crater Flat Group) at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Moyer, T.C.; Geslin, J.K.

1995-01-01

Lithostratigraphic relations within the Calico Hills Formation and Prow Pass Tuff (Crater Flat Group) were reconstructed from analysis of core samples and observation of outcrop exposures. The Calico Hills Formation is composed of five nonwelded pyroclastic units (each formed of one or more pyroclastic-flow deposits) that overlie an interval of bedded tuff and a basal volcaniclastic sandstone unit. The Prow Pass Tuff is divided into four pyroclastic units and an underlying interval of bedded tuff. The pyroclastic units of the Prow Pass Tuff are distinguished by the sizes and amounts of their pumice and lithic clasts and their degree of welding. Pyroclastic units of the Prow Pass Tuff are distinguished from those of the Calico Hills Formation by their phenocryst assemblage, chemical composition, and ubiquitous siltstone lithic clasts. Downhole resistivity tends to mirror the content of authigenic minerals, primarily zeolites, in both for-mations and may be useful for recognizing the vitric-zeolite boundary in the study area. Maps of zeolite distribution illustrate that the bedded tuff and basal sandstone units of the Calico Hills Formation are altered over a wider area than the pyroclastic units of both the Calico Hills Formation and the upper Prow Pass Tuff

Lithostratigraphy of the Calico Hills Formation and Prow Pass Tuff (Crater Flat Group) at Yucca Mountain, Nevada

Energy Technology Data Exchange (ETDEWEB)

Moyer, T.C.; Geslin, J.K. [Science Applications International Corp., Las Vegas, NV (United States)

1995-07-01

Lithostratigraphic relations within the Calico Hills Formation and Prow Pass Tuff (Crater Flat Group) were reconstructed from analysis of core samples and observation of outcrop exposures. The Calico Hills Formation is composed of five nonwelded pyroclastic units (each formed of one or more pyroclastic-flow deposits) that overlie an interval of bedded tuff and a basal volcaniclastic sandstone unit. The Prow Pass Tuff is divided into four pyroclastic units and an underlying interval of bedded tuff. The pyroclastic units of the Prow Pass Tuff are distinguished by the sizes and amounts of their pumice and lithic clasts and their degree of welding. Pyroclastic units of the Prow Pass Tuff are distinguished from those of the Calico Hills Formation by their phenocryst assemblage, chemical composition, and ubiquitous siltstone lithic clasts. Downhole resistivity tends to mirror the content of authigenic minerals, primarily zeolites, in both for-mations and may be useful for recognizing the vitric-zeolite boundary in the study area. Maps of zeolite distribution illustrate that the bedded tuff and basal sandstone units of the Calico Hills Formation are altered over a wider area than the pyroclastic units of both the Calico Hills Formation and the upper Prow Pass Tuff.

Business System Planning Project, Preliminary System Design

International Nuclear Information System (INIS)

EVOSEVICH, S.

2000-01-01

CH2M HILL Hanford Group, Inc. (CHG) is currently performing many core business functions including, but not limited to, work control, planning, scheduling, cost estimating, procurement, training, and human resources. Other core business functions are managed by or dependent on Project Hanford Management Contractors including, but not limited to, payroll, benefits and pension administration, inventory control, accounts payable, and records management. In addition, CHG has business relationships with its parent company CH2M HILL, U.S. Department of Energy, Office of River Protection and other River Protection Project contractors, government agencies, and vendors. The Business Systems Planning (BSP) Project, under the sponsorship of the CH2M HILL Hanford Group, Inc. Chief Information Officer (CIO), have recommended information system solutions that will support CHG business areas. The Preliminary System Design was developed using the recommendations from the Alternatives Analysis, RPP-6499, Rev 0 and will become the design base for any follow-on implementation projects. The Preliminary System Design will present a high-level system design, providing a high-level overview of the Commercial-Off-The-Shelf (COTS) modules and identify internal and external relationships. This document will not define data structures, user interface components (screens, reports, menus, etc.), business rules or processes. These in-depth activities will be accomplished at implementation planning time

Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br

Science.gov (United States)

Hsu, H-J.; DeMore, W.

1994-01-01

Rate constants for the reactions of OH with CH3C1, CH2Cl2, CHCl3 and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2)and for CH2Cl2, HFC-161 (CH3CH2F).

Kinematic analysis of the flight phase of the Nordic combined and ski jump on a large hill (HS-134 m) during the 2009 Nordic World Ski Championships.

Science.gov (United States)

Svoboda, Zdenek; Janura, Miroslav; Cabell, Lee; Janurová, Eva

2011-01-01

The purpose of this study was to assess the execution of the flight phase in the Nordic combined (NC) among three groups of competitors, representing different skill levels, and to compare them with three groups of ski jumpers (SJs). Thirty NC and thirty SJ competitors, who performed ski jumps on an HS-134 m jumping hill, were divided into three subgroups based on jump length execution. Two-dimensional (2-D) kinematic data were collected from the lower extremities, trunks, and skis of the competitors. The SJ group had a smaller lower extremity angle ( p jump lengths comparable to those of the SJ competitors by having significantly higher in-run velocities.

Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5).

Science.gov (United States)

Currie, Fredrik; Jarvoll, Patrik; Holmberg, Krister; Romsted, Laurence S; Gunaseelan, Krishnan

2007-08-15

High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tan, Yee Seng; Halim, Siti Nadiah Abdul [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Tiekink, Edward R.T. [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Sunway Univ., Bandar Sunway (Malaysia). Centre for Chemical Crystallography

2016-04-01

Crystallization of Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2} from ethanol yields the coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}.EtOH]{sub ∞} (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ{sub 2}κ{sup 2}-tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ{sub 2}κ{sup 2}-tridentate as for 1 but the other two being κ{sup 2}-chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 3}.MeCN]{sub ∞} and binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2H{sub 2}O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}:2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{sub 4}[SO{sub 4}]{sub 2}{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} (4) and the salt [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{Cd[S_2CN(iPr)CH_2CH_2OH]_3} (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

Science.gov (United States)

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.

Science.gov (United States)

Carrasco, Erica; Smith, Kenneth J; Meloni, Giovanni

2018-01-11

The reactions of furan and 2-methylfuran with methylidyne CH (X 2 Π) radical were investigated at 298 K using synchrotron radiation produced at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Reaction products were observed by multiplexed photoionization mass spectrometry and characterized based on their photoionization spectra and kinetic time traces. Primary products observed in furan + CH are 2,4-cyclopentadien-1-one (m/z = 80), 2-penten-4-ynal (m/z = 80), and vinylacetylene (m/z = 52). From 2-methylfuran + CH, 2-4-cyclopentadien-1-carbaldehyde (m/z = 94), 2,3,4-hexatrienal (m/z = 94), 1,3 cyclopentadiene (m/z = 66), 3-penten-1-yne (Z) (m/z = 66), and vinylacetylene (m/z = 52) are the primary products observed. Using potential energy surface scans, thermodynamically favorable reaction pathways are proposed. CH addition to the π-bonds in furan and 2-methylfuran rings was found to be the entrance channel that led to formation of all identified primary products. Both reactions follow patterns of H loss and CHO loss, as well as formation of cyclic and acyclic isomers.

The Origin of the Columbia Hills

Science.gov (United States)

Rice, J. W.

2005-12-01

The Columbia Hills form a rugged ridge complex comprised of 7 peaks spanning some 3.5 km in length and reaching a maximum height of 106 m (Husband Hill) above the plains of Spirit's landing site. As of this writing Spirit has been exploring the Columbia Hills for over 440 sols (since sol 156 on June 11, 2004). Thus far the origin of the Columbia Hills has remained elusive despite detailed analysis of numerous rock and soil targets, including outcrops. The chemical differences among the 6 distinct rock classes attest to the lithologic diversity and geologic complexity of the Hills. Origin of the Columbia Hills Several hypothesis have been put forth to explain the origin of the Columbia Hills: Old eroded partially buried impact crater rim(s), central peak, residual intracrater fill material, volcanic construct, wrinkle ridge, delta and or combinations of the above. Observations that support various aspects of these multiple hypotheses will be discussed. Numerous buried craters are observed on the floor of Gusev lending credence to the idea that the Columbia Hills are the remains of an ancient impact crater rim or possibly a central peak. Morphologic evidence of the rim of Thira crater and the Columbia Hills appears to support this hypothesis. The Aeolis region contains numerous craters that contain layered materials in the absence of any major fluvial systems. This could imply that the Columbia Hills are the remnants of a formerly extensive unit(s). Gusev contains many hills scattered across its floor such as Grissom, White, Chaffee and numerous other buttes and mesas that may be remnants of a former extensive intracrater deposit. Another possibility is that the Columbia Hills are composed of volcanic materials (cinder cones and associated ash and lava flows) derived either locally or from Apollinaris Patera located 300 km to the north. Several depressions are located in the Columbia Hills. These features could be calderas but are most likely impact craters. The most

Inorganic soil and groundwater chemistry near Paducah Gaseous Diffusion Plant, Paducah, Kentucky

Energy Technology Data Exchange (ETDEWEB)

Moore, G.K. [Tennessee Univ., Knoxville, TN (United States)

1995-03-01

Near-surface soils, boreholes, and sediments near the Paducah Gaseous Diffusion Plant (PGDP) were sampled in 1989-91 as were monitoring wells, TVA wells, and privately-owned wells. Most wells were sampled two or three times. The resulting chemical analyses have been published in previous reports and have been previously described (CH2M HILL 1991, 1992; Clausen et al. 1992). The two reports by CH2M HILL are controversial, however, because, the concentrations of some constituents were reported to exceed background levels or drinking water standards and because both on-site (within the perimeter fence at PGDP) and off-site pollution was reported to have occurred. The groundwater samples upon which these interpretations were based may not be representative, however. The CH2M HILL findings are discussed in the report. The purpose of this report is to characterize the inorganic chemistry of groundwater and soils near PGDP, using data from the CH2M HILL reports (1991, 1992), and to determine whether or not any contamination has occurred. The scope is limited to analysis and interpretation of data in the CH2M HILL reports because previous interpretations of these data may not be valid, because samples were collected in a relatively short period of time at several hundred locations, and because the chemical analyses are nearly complete. Recent water samples from the same wells were not considered because the characterization of inorganic chemistry for groundwater and soil requirements only one representative sample and an accurate analysis from each location.

Inorganic soil and groundwater chemistry near Paducah Gaseous Diffusion Plant, Paducah, Kentucky

International Nuclear Information System (INIS)

Moore, G.K.

1995-03-01

Near-surface soils, boreholes, and sediments near the Paducah Gaseous Diffusion Plant (PGDP) were sampled in 1989-91 as were monitoring wells, TVA wells, and privately-owned wells. Most wells were sampled two or three times. The resulting chemical analyses have been published in previous reports and have been previously described (CH2M HILL 1991, 1992; Clausen et al. 1992). The two reports by CH2M HILL are controversial, however, because, the concentrations of some constituents were reported to exceed background levels or drinking water standards and because both on-site (within the perimeter fence at PGDP) and off-site pollution was reported to have occurred. The groundwater samples upon which these interpretations were based may not be representative, however. The CH2M HILL findings are discussed in the report. The purpose of this report is to characterize the inorganic chemistry of groundwater and soils near PGDP, using data from the CH2M HILL reports (1991, 1992), and to determine whether or not any contamination has occurred. The scope is limited to analysis and interpretation of data in the CH2M HILL reports because previous interpretations of these data may not be valid, because samples were collected in a relatively short period of time at several hundred locations, and because the chemical analyses are nearly complete. Recent water samples from the same wells were not considered because the characterization of inorganic chemistry for groundwater and soil requirements only one representative sample and an accurate analysis from each location

Methane Provenance Determined by CH2D2 and 13CH3D Abundances

Science.gov (United States)

Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.

2017-12-01

Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

Soil CO2, CH4 and N2O effluxes and concentrations in soil profiles down to 15.5m depth in eucalypt plantations under contrasted rainfall regimes

Science.gov (United States)

Germon, A.; Nouvellon, Y.; Christophe, J.; Chapuis-Lardy, L.; Robin, A.; Rosolem, C. A.; Gonçalves, J. L. D. M.; Guerrini, I. A.; Laclau, J. P.

2017-12-01

Silvicultural practices in planted forests affect the fluxes of greenhouse gases at the soil surface and the major factors driving greenhouse gas production in forest soils (substrate supply, temperature, water content,…) vary with soil depth. Our study aimed to assess the consequences of drought on the temporal variability of CO2, CH4 and N2O fluxes throughout very deep soil profiles in Eucalyptus grandis plantations 3 months before the harvest then in coppice, the first 18 months after clear-cutting. Two treatments were compared: one with 37% of throughfall excluded by plastic sheets (TE), and one without rainfall exclusion (WE). Measurements of soil CO2 efflux were made every two weeks for 30 months using a closed-path Li8100 system in both treatment. Every two weeks for 21 months, CO2, CH4 and N2O surface effluxes were measured using the closed-chamber method and concentrations in the soil were measured at 7 depths down to 15.5 m in both TE and WE. At most measurement dates, soil CO2 efflux were significantly higher in TE than in WE. Across the two treatments and the measurement dates, CO2 concentrations increased from 4446 ± 2188 ppm at 10 cm deep to 15622 ± 3523 ppm at 15.5 m, CH4 concentrations increased from 0.41 ± 0.17 ppm at 10 cm deep to 0.77 ± 0.24 ppm at 15.5 m and N2O concentrations remained roughly constant and were on average 478 ± 55 ppb between soil surface and 15.5 m deep. CO2 and N2O concentrations were on average 20.7 and 7.6% lower in TE than in WE, respectively, across the sampling depths. However, CH4 concentrations in TE were on average 44.4% higher than in WE, throughout the soil profile. Those results suggest that extended drought periods might reduce the production of CO2 and N2O but increase the accumulation of CH4 in eucalypt plantations established in deep tropical soils. Very deep tropical soils cover huge areas worldwide and improving our understanding of the spatiotemporal dynamics of gas concentrations in deep soil layers

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

DEFF Research Database (Denmark)

Hurley, MD; Ball, JC; Wallington, TJ

2004-01-01

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH...... respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration......, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27...

OH yields from the CH3CO+O-2 reaction using an internal standard\\ud

OpenAIRE

Carr, S.A.; Baeza-Romero, M.T.; Blitz, M.A.; Pilling, M.J.; Heard, D.E.; Seakins, P.W.

2007-01-01

Laser flash photolysis of CH3C(O)OH at 248 nm was used to create equal zero time yields of CH3CO and OH. The absolute OH yield from the CH3CO + O2 (+M) reaction was determined by following the OH temporal profile using the zero time\\ud OH concentration as an internal standard. The OH yield from CH3CO + O2 (+M) was observed to decrease with increasing pressure with an extrapolated zero pressure yield\\ud close to unity (1.1 ± 0.2, quoted uncertainties correspond to 95% confidence limits). The r...

River Protection Project (RPP) Readiness-to-Proceed 2 Internal Independent Review Team Final Report

International Nuclear Information System (INIS)

SCHAUS, P.S.

2000-01-01

This report describes the results of an independent review team brought in to assess CH2M HILL Hanford's readiness and ability to support the RPP's move into its next major phase - retrieval and delivery of tank waste to the Privatization Contractor

Utilisation of an eta(3)-allyl hydride complex, formed by UV irradiation, as a controlled source of 16-electron (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

Science.gov (United States)

Sexton, Catherine J; López-Serrano, Joaquín; Lledós, Agustí; Duckett, Simon B

2008-10-21

Low temperature UV irradiation of solutions of (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe)(2) yields (eta(5)-C(5)Me(5))Rh(eta(3)-CH(2)CHCH(2))(H), which provides controlled access to the 16-electron fragment (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

UAVSAR observations of triggered slip on the Imperial, Superstition Hills, and East Elmore Ranch Faults associated with the 2010 M 7.2 El Mayor-Cucapah earthquake

Science.gov (United States)

Donnellan, Andrea; Parker, Jay; Hensley, Scott; Pierce, Marlon; Wang, Jun; Rundle, John

2014-03-01

4 April 2010 M 7.2 El Mayor-Cucapah earthquake that occurred in Baja California, Mexico and terminated near the U.S. Mexican border caused slip on the Imperial, Superstition Hills, and East Elmore Ranch Faults. The pattern of slip was observed using radar interferometry from NASA's Uninhabited Aerial Vehicle Synthetic Aperture Radar (UAVSAR) instrument collected on 20-21 October 2009 and 12-13 April 2010. Right-lateral slip of 36 ± 9 and 14 ± 2 mm occurred on the Imperial and Superstition Hills Faults, respectively. Left-lateral slip of 9 ± 2 mm occurred on the East Elmore Ranch Fault. The widths of the zones of displacement increase northward suggesting successively more buried fault motion to the north. The observations show a decreasing pattern of slip northward on a series of faults in the Salton Trough stepping between the El Mayor-Cucapah rupture and San Andreas Fault. Most of the motion occurred at the time of the M 7.2 earthquake and the UAVSAR observations are consistent with field, creepmeter, GPS, and Envisat observations. An additional 28 ± 1 mm of slip at the southern end of the Imperial Fault over a <1 km wide zone was observed over a 1 day span a week after the earthquake suggesting that the fault continued to slip at depth following the mainshock. The total moment release on the three faults is 2.3 × 1023-1.2 × 1024 dyne cm equivalent to a moment magnitude release of 4.9-5.3, assuming shallow slip depths ranging from 1 to 5 km.

SURVEY OBSERVATIONS OF A POSSIBLE GLYCINE PRECURSOR, METHANIMINE (CH{sub 2}NH)

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Taiki; Ohishi, Masatoshi; Hirota, Tomoya; Saito, Masao [Department of Astronomy, the Graduate University for Advanced Studies (SOKENDAI), Osawa 2-21-1, Mitaka, Tokyo 181-8588 (Japan); Majumdar, Liton; Wakelam, Valentine, E-mail: taiki.suzuki@nao.ac.jp [Univ. Bordeaux, LAB, UMR 5804, F-33270, Floirac (France)

2016-07-01

We conducted survey observations of a glycine precursor, methanimine, or methylenimine (CH{sub 2}NH), with the Nobeyama Radio Observatory 45 m telescope and the Sub-Millimeter Radio telescope toward 12 high-mass and two low-mass star-forming regions in order to increase the number of known CH{sub 2}NH sources and to better understand the characteristics of CH{sub 2}NH sources. As a result of our survey, CH{sub 2}NH was detected in eight sources, including four new sources. The estimated fractional abundances were ∼10{sup −8} in Orion KL and G10.47+0.03, while they were ∼10{sup −9} toward the other sources. Our hydrogen recombination line and past studies suggest that CH{sub 2}NH-rich sources have less (this mean not so evolved) evolved H ii regions. The lower destruction rates from UV flux from the central star would contribute to the high CH{sub 2}NH abundances toward CH{sub 2}NH-rich sources. Our gas-grain chemical simulations suggest that CH{sub 2}NH is mostly formed in the gas phase by neutral–neutral reactions, rather than being the product of thermal evaporation from dust surfaces.

Characterization of Vadose Zone Sediments from C Waste Management Area: Investigation of the C-152 Transfer Line Leak

Energy Technology Data Exchange (ETDEWEB)

Brown, Christopher F.; Serne, R. Jeffrey; Bjornstad, Bruce N.; Valenta, Michelle M.; Lanigan, David C.; Vickerman, Tanya S.; Clayton, Ray E.; Geiszler, Keith N.; Iovin, Cristian; Clayton, Eric T.; Kutnyakov, Igor V.; Baum, Steven R.; Lindberg, Michael J.; Orr, Robert D.

2008-09-11

The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in January 2007. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at Hanford. To meet this goal, CH2M HILL Hanford Group, Inc., tasked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within waste management area (WMA) C. Specifically, this report contains all the geologic, geochemical, and selected physiochemical characterization data compiled on vadose zone sediment recovered from direct-push samples collected around the site of an unplanned release (UPR), UPR-200-E-82, adjacent to the 241-C-152 Diversion Box located in WMA C.

New cascade laser transitions in CH2F2 pumped with the 9R32 line of a cw CO2 laser

International Nuclear Information System (INIS)

Nieswand, C.

1991-11-01

New cascade laser transitions of 12 CH 2 F 2 at 172.50μm, 208.83μm, 220.44μm, 223.99μm,and 250.61μm are reported. A waveguide FIR laser was pumped with a quasi cw 12 C 16 O 2 laser operating on the 9R32 line. Together with the already known lines at 184.3μm, 196.1μm and 235.9μm, the laser lines can be assigned to rotational transitions in the ν 9 vibrational band of 12 CH 2 F 2 and to refill transitions of the vibrational ground state ν 0 . 1 fig., 2 tabs., 6 refs. (author)

Ethanol oxidation reactions catalyzed by water molecules: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2)

Science.gov (United States)

Takahashi, H.; Hisaoka, S.; Nitta, T.

2002-09-01

Ab initio density functional theory calculations have been performed to investigate the catalytic role of water molecules in the oxidation reaction of ethanol: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2) . The results show that the potential energy barrier for the reaction is 88.0 kcal/mol in case of n=0, while it is reduced by ˜34 kcal/mol when two water molecules are involved ( n=2) in the reaction. As a result, the rate constant increases to 3.31×10 -4 s-1, which shows a significant catalytic role of water molecules in the ethanol oxidation reactions.

Rational design of organic superconductors through the use of the large, discrete molecular anions M(CF3)4-(M = Cu, Ag, Au) and SO3CF2CH2SF5-

International Nuclear Information System (INIS)

Schlueter, J.A.; Geiser, U.; Williams, J.M.

1996-01-01

A new approach to synthesis of organic superconductors has recently been pioneered which involves the use of large discrete molecular anions as the charge-compensating entities in these charge transfer salts. The organic electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) has been electrocrystallized with the novel organometallic M(CF 3 ) 4 - (M=Cu, Ag, Au) anions in a variety of 1,1,2-trihaloethane solvents. Over 20 organic superconductors have been synthesized which can be described by (ET) 2 M(CF 3 ) 4 (1,1,2- trihaloethane). These solvated salts are shown to have highly anisotropic physical properties which can be tuned via modifications of each of their three molecular components: ET electron donor molecule, M(CF 3 ) 4 - anion, and neutral 1,1,2- trihaloethane solvent molecule. Superconductivity has also been observed in an ET salt containing the discrete SF 5 CH 2 CF 2 SO 3 - anion with onset temperature near 5.2 K

Characterization of Vadose Zone Sediments Below the C Tank Farm: Borehole C4297 and RCRA Borehole 299-E27-22

International Nuclear Information System (INIS)

Brown, Christopher F.; Serne, R. Jeffrey; Bjornstad, Bruce N.; Horton, Duane G.; Lanigan, David C.; Clayton, Ray E.; Valenta, Michelle M.; Vickerman, Tanya S.; Kutnyakov, Igor V.; Geiszler, Keith N.; Baum, Steven R.; Parker, Kent E.; Lindberg, Michael J.

2008-01-01

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.7 and 4.25. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in September 2006. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at the Hanford Site. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory (PNNL) to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) C. This report is the first of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physiochemical characterization data collected on vadose zone sediment recovered from borehole C4297, installed adjacent to tank C-105, and from borehole 299-E27-22, installed directly north of the C Tank Farm. This report also presents the interpretation of data in the context of sediment types, the vertical extent of contamination, the migration potential of the contaminants, and the likely source of the contamination in the vadose zone below the C Tank Farm. The information presented in this report supports the WMA A-AX, C, and U field investigation report in preparation by CH2M HILL Hanford Group, Inc

Characterization of Vadose Zone Sediments Below the C Tank Farm: Borehole C4297 and RCRA Borehole 299-E27-22

Energy Technology Data Exchange (ETDEWEB)

Brown, Christopher F.; Serne, R. Jeffrey; Bjornstad, Bruce N.; Horton, Duane G.; Lanigan, David C.; Clayton, Ray E.; Valenta, Michelle M.; Vickerman, Tanya S.; Kutnyakov, Igor V.; Geiszler, Keith N.; Baum, Steven R.; Parker, Kent E.; Lindberg, Michael J.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.7 and 4.25. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in September 2006. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at the Hanford Site. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory (PNNL) to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) C. This report is the first of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physiochemical characterization data collected on vadose zone sediment recovered from borehole C4297, installed adjacent to tank C-105, and from borehole 299-E27-22, installed directly north of the C Tank Farm. This report also presents the interpretation of data in the context of sediment types, the vertical extent of contamination, the migration potential of the contaminants, and the likely source of the contamination in the vadose zone below the C Tank Farm. The information presented in this report supports the WMA A-AX, C, and U field investigation report in preparation by CH2M HILL Hanford Group, Inc.

Background CH4 and N2O fluxes in low-input short rotation coppice

Science.gov (United States)

Görres, Carolyn-Monika; Zenone, Terenzio; Ceulemans, Reinhart

2016-04-01

Extensively managed short rotation coppice systems are characterized by low fluxes of CH4 and N2O. However due to the large global warming potential of these trace gases (GWP100: CH4: 34, N2O: 298), such background fluxes can still significantly contribute to offsetting the CO2 uptake of short rotation coppice systems. Recent technological advances in fast-response CH4 and N2O analysers have improved our capability to capture these background fluxes, but their quantification still remains a challenge. As an example, we present here CH4 and N2O fluxes from a short-rotation bioenergy plantation in Belgium. Poplars have been planted in a double-row system on a loamy sand in 2010 and coppiced in the beginning of 2012 and 2014 (two-year rotation system). In 2013 (June - November) and 2014 (April - August), the plantation's CH4 and N2O fluxes were measured in parallel with an eddy covariance tower (EC) and an automated chamber system (AC). The EC had a detection limit of 13.68 and 0.76 μmol m-2 h-1 for CH4 and N2O, respectively. The median detection limit of the AC was 0.38 and 0.08 μmol m-2 h-1 for CH4 and N2O, respectively. The EC picked up a few high CH4 emission events with daily averages >100 μmol m-2 h-1, but a large proportion of the measured fluxes were within the EC's detection limit. The same was true for the EC-derived N2O fluxes where the daily average flux was often close to the detection limit. Sporadically, some negative (uptake) fluxes of N2O were observed. On the basis of the EC data, no clear link was found between CH4 and N2O fluxes and environmental variables. The problem with fluxes within the EC detection limit is that a significant amount of the values can show the opposite sign, thus "mirroring" the true flux. Subsequently, environmental controls of background trace gas fluxes might be disguised in the analysis. As a next step, it will be tested if potential environmental drivers of background CH4 and N2O fluxes at the plantation can be

SYNTHESIS AND CHARACTERIZATION OF (MU-5-C5ME5)2TI(R)CL (R = ME, ET, NORMAL-PR, CH=CH2, PH, O-NORMAL-PR) AND THEIR SALT METATHESIS REACTIONS - THERMAL-DECOMPOSITION PATHWAYS OF (MU-5-C5ME5)2TI(ME)R' (R' = ET, CH=CH2, PH, CH2PH)

NARCIS (Netherlands)

LUINSTRA, GA; TEUBEN, JH

Complexes Cp*2Ti(R)Cl (Cp* = eta-5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (4), Ph (5), O-n-Pr (6)) have been prepared by oxidation Of CP*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R. was observed. Homolysis of

Synthesis and Characterization of (η5-C5Me5)2Ti(R)Cl (R = Me, Et, n-Pr, CH=CH2, Ph, O-n-Pr) and Their Salt Metathesis Reactions. Thermal Decomposition Pathways of (η5-C5Me5)2Ti(Me)R' (R' = Et, CH=CH2, Ph, CH2Ph)

NARCIS (Netherlands)

Luinstra, Gerrit A.; Teuben, Jan H.

1992-01-01

Complexes Cp*2Ti(R)Cl (Cp* = η5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (41, Ph (5), O-n-Pr (6)) have been prepared by oxidation of Cp*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R· was observed. Homolysis of

Metal ion displacements in noncentrosymmetric chalcogenides La{sub 3}Ga{sub 1.67}S{sub 7}, La{sub 3}Ag{sub 0.6}GaCh{sub 7} (Ch=S, Se), and La{sub 3}MGaSe{sub 7} (M=Zn, Cd)

Energy Technology Data Exchange (ETDEWEB)

Iyer, Abishek K. [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G2G2 (Canada); Yin, Wenlong [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G2G2 (Canada); Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900 (China); Rudyk, Brent W. [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G2G2 (Canada); Lin, Xinsong [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G2G2 (Canada); Centre for Oil Sands Sustainability, Northern Alberta Institute of Technology, Edmonton, Alberta, Canada T6N1E5 (Canada); Nilges, Tom [Department of Chemistry, Technical University of Munich, 85748 Garching b. München (Germany); Mar, Arthur, E-mail: arthur.mar@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G2G2 (Canada)

2016-11-15

The quaternary Ga-containing chalcogenides La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}, La{sub 3}ZnGaSe{sub 7}, and La{sub 3}CdGaSe{sub 7}, as well as the related ternary chalcogenide La{sub 3}Ga{sub 1.67}S{sub 7}, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P6{sub 3}, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La{sub 3}M{sub 1–x}GaCh{sub 7} (M=Ga, Ag, Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced. - Graphical abstract: Partial occupation of metal atoms in multiple sites accounts for versatility in Ga-containing chalcogenides La{sub 3}M{sub 1–x}GaCh{sub 7} with noncentrosymmetric hexagonal structures. - Highlights: • La{sub 3}M{sub 1–x}GaCh{sub 7} (M =Ga, Ag, Zn, Cd; Ch =S, Se) adopt related hexagonal structures. • Large displacements of M atoms originate from partial occupation of multiple

Hanford Site River Protection Project (RPP) High-Level Waste Storage

International Nuclear Information System (INIS)

KRISTOFZSKI, J.G.

2000-01-01

The CH2M HILL Hanford Group (CHG) conducts business to achieve the goals of the U.S. Department of Energy's (DOE) Office of River Protection at the Hanford Site. The CHG is organized to manage and perform work to safely store, retrieve, etc

Release of CO{sub 2} and CH{sub 4} from small wetland lakes in western Siberia

Energy Technology Data Exchange (ETDEWEB)

Repo, M.E.; Huttunen, J.T.; Martikainen, P.J. [Univ. of Kuopio, Dept. of Env ironmental Science, FI-70211 Kuopio (Finland); Naumov, A.V.; Chichulin, A.V. [I nst. of Soil Science and Agrochemistry, Russian Academy of Science, 630099 Novos ibirsk (Russian Federation); Lapshina, E.D. [Yugra State Univ., 628012, Khanty-Mansiysk (Russian Federation); Bleuten , W. [Utrecht Univ., Dept. of Physical Geography,3508 TC Utrecht (Netherlands)

2007-11-15

CO{sub 2} and CH{sub 4} fluxes were measured from three small wetland lakes located in the middle taiga and forest tundra zones on West Siberian Lowlands (WSL), the world's largest wetland area. Fluxes were measured during summer 2005 using floating chambers and were validated against the thin boundary layer model based on the relationship between gas exchange and wind speed. All studied lakes were supersaturated with CO{sub 2} and CH{sub 4}, and acted on a seasonal basis as sources of these greenhouse gases to the atmosphere. Daily mean CO{sub 2} fluxes measured with chambers ranged from near the zero to 3.1 g CO{sub 2}/m{sup 2}/d and corresponding CH{sub 4} fluxes from 1.1 to 120 mg CH{sub 4}/m{sup 2}/d. CH{sub 4} ebullition (0.65-11 mg CH{sub 4}/m{sup 2}/d) was detected in two of the lakes. Total carbon evasion from the studied lakes during the active season was 23-66 g C/m{sup 2}, of which more than 90% was released as CO{sub 2}-C. The carbon loss per unit area from the studied lakes was of similar magnitude as previously reported values of net carbon uptake of Siberian peatlands. This emphasizes the importance of small water-bodies in the carbon balance of West Siberian landscape.

Funny hills in pion spectra from heavy-ion collisions

International Nuclear Information System (INIS)

Rasmussen, J.O.

1982-03-01

A discussion of some of the systematic features of the pion spectra in heavy-ions reactions is given. A discussion of the hills and valleys in heavy ion pion spectra that show up at the lower pion energies is given. The following topics are discussed: (1) three kinds of funny hills; (2) π - / + ratios near center of mass; (3) new Monte Carlo studies of charged pion spectra; and (4) pion orbiting about fireballs and Bose-Einstein behavior as explanation for the mid-rapidity P/sub perpendicular to/ approx. = 0.4 to 0.5 m/sub π/c hill

Atmospheric chemistry of CH3CHF2 (R-152a): mechanism of the CH3CF2O2+HO2 reaction

DEFF Research Database (Denmark)

Hashikawa, Y; Kawasaki, M; Andersen, Mads Peter Sulbæk

2004-01-01

FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed with resp......FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed...

Gully hotspot contribution to landscape methane (CH4) and carbon dioxide (CO2) fluxes in a northern peatland

International Nuclear Information System (INIS)

McNamara, N.P.; Plant, T.; Oakley, S.; Ward, S.; Wood, C.; Ostle, N.

2008-01-01

Peatlands are long term carbon catchments that sink atmospheric carbon dioxide (CO 2 ) and source methane (CH 4 ). In the uplands of the United Kingdom ombrotrophic blanket peatlands commonly exist within Calluna vulgaris (L.) dominated moorland ecosystems. These landscapes contain a range of topographical features that influence local hydrology, climate and plant community composition. In this study we examined the variation in ecosystem CO 2 respiration and net CH 4 fluxes from typical plant-soil systems in dendritic drainage gullies and adjacent blanket peat during the growing season. Typically, Eriophorum spp., Sphagnum spp. and mixed grasses occupied gullies while C. vulgaris dominated in adjacent blanket peat. Gross CO 2 respiration was highest in the areas of Eriophorum spp. (650 ± 140 mg CO 2 m -2 h -1 ) compared to those with Sphagnum spp. (338 ± 49 mg CO 2 m -2 h -1 ), mixed grasses (342 ± 91 mg CO 2 m -2 h -1 ) and C. vulgaris (174 ± 63 mg CO 2 m -2 h -1 ). Measurements of the net CH 4 flux showed higher fluxes from the Eriophorum spp (2.2 ± 0.6 mg CH 4 m -2 h -1 ) locations compared to the Sphagnum spp. (0.6 ± 0.4 mg CH 4 m -2 h -1 ), mixed grasses (0.1 ±0.1 mg CH 4 m -2 h -1 ) and a negligible flux detected from C. vulgaris (0.0 ± 0.0 mg CH 4 m -2 h -1 ) locations. A GIS approach was applied to calculate the contribution of gullies to landscape scale greenhouse gas fluxes. Findings from the Moor House National Nature Reserve in the UK showed that although gullies occupied only 9.3% of the total land surface, gullies accounted for 95.8% and 21.6% of the peatland net CH 4 and CO 2 respiratory fluxes, respectively. The implication of these findings is that the relative contribution of characteristic gully systems need to be considered in estimates of landscape scale peatland greenhouse gas fluxes

Automatizace útoku MitM na WiFi sítích

OpenAIRE

Vondráček, Martin

2016-01-01

Tato bakalářská práce se zaměřuje na výzkum v oblasti bezpečnosti bezdrátových sítí. Práce přináší studii široce využívaných síťových technologií a principů zajištění bezpečnosti bezdrátových sítí. Analyzované technologie a způsoby zabezpečení trpí slabinami, které mohou být zneužity k provedení útoku MitM . Práce zahrnuje přehled dostupných nástrojů zaměřených na využití jednotlivých slabin. Výsledkem této práce je balíček wifimitm a CLI nástroj, oba implementované v jazyce Python. Balíček p...

1.2V, 24mW/ch, 10bit, 80MSample/s Pipelined A/D Converters

Science.gov (United States)

Ueno, Takeshi; Ito, Tomohiko; Kurose, Daisuke; Yamaji, Takafumi; Itakura, Tetsuro

This paper describes 10-bit, 80-MSample/s pipelined A/D converters for wireless-communication terminals. To reduce power consumption, we employed the I/Q amplifier sharing technique [1] in which an amplifier is used for both I and Q channels. In addition, common-source, pseudo-differential (PD) amplifiers are used in all the conversion stages for further power reduction. Common-mode disturbances are removed by the proposed common-mode feedforward (CMFF) technique without using fully differential (FD) amplifiers. The converter was implemented in a 90-nm CMOS technology, and it consumes only 24mW/ch from a 1.2V power supply. The measured SNR and SNDR are 58.6dB and 52.2dB, respectively.

Large CO2 and CH4 release from a flooded formerly drained fen

Science.gov (United States)

Sachs, T.; Franz, D.; Koebsch, F.; Larmanou, E.; Augustin, J.

2016-12-01

Drained peatlands are usually strong carbon dioxide (CO2) sources. In Germany, up to 4.5 % of the national CO2 emissions are estimated to be released from agriculturally used peatlands and for some peatland-rich northern states, such as Mecklenburg-Western Pomerania, this share increases to about 20%. Reducing this CO2 source and restoring the peatlands' natural carbon sink is one objective of large-scale nature protection and restoration measures, in which 37.000 ha of drained and degraded peatlands in Mecklenburg-Western Pomerania are slated for rewetting. It is well known, however, that in the initial phase of rewetting, a reduction of the CO2 source strength is usually accompanied by an increase in CH4 emissions. Thus, whether and when the intended effects of rewetting with regard to greenhouse gases are achieved, depends on the balance of CO2 and CH4 fluxes and on the duration of the initial CH4 emission phase. In 2013, a new Fluxnet site went online at a flooded formerly drained river valley fen site near Zarnekow, NE Germany (DE-Zrk), to investigate the combined CO2 and CH4 dynamics at such a heavily degraded and rewetted peatland. The site is dominated by open water with submerged and floating vegetation and surrounding Typha latifolia.Nine year after rewetting, we found large CH4 emissions of 53 g CH4 m-2 a-1 from the open water area, which are 4-fold higher than from the surrounding vegetation zone (13 g CH4 m-2 a-1). Surprisingly, both the open water and the vegetated area were net CO2 sources of 158 and 750 g CO2 m-2 a-1, respectively. Unusual meteorological conditions with a warm and dry summer and a mild winter might have facilitated high respiration rates, particularly from temporally non-inundated organic mud in the vegetation zone.

Ultraviolet absorption spectra and kinetics of CH3S and CH2SH radicals

DEFF Research Database (Denmark)

Anastasi, C.; Broomfield, M.; Nielsen, O.J.

1991-01-01

The ultraviolet absorption spectra of CH3S and CH2SH radicals have been measured between 215 and 380 nm using the pulse-radiolysis/kinetic-absorption method. One absorption band between 250 and 300 nm and one around 215 nm have been tentatively assigned to the CH2SH and CH3S radicals, respectively....... This spectrum has been used to measure the self-reaction rates of these radicals. Rate constants of 4 x 10(-11) and 7 x 10(-11) cm3 molecule-1 s-1 have been measured at 298 K for CH3S and CH2SH recombination, respectively. The possible reaction pathways are discussed....

Managing Waste Inventory and License Limits at the Perma-Fix Northwest Facility to Meet CH2M Hill Plateau Remediation Company (CHPRC) American Recovery and Reinvestment Act (ARRA) Deliverables - 12335

Energy Technology Data Exchange (ETDEWEB)

Moak, Don J.; Grondin, Richard L. [Perma-Fix Environmental Services, Inc. - PESI, Richland, WA 99354 (United States); Triner, Glen C.; West, Lori D. [East Tennessee Materials and Energy Corporation - M and EC, Richland, WA 99354 (United States)

2012-07-01

CH2M Hill Plateau Remediation Company (CHRPC) is a prime contractor to the U.S. Department of Energy (DOE) focused on the largest ongoing environmental remediation project in the world at the DOE Hanford Site Central Plateau, i.e. the DOE Hanford Plateau Remediation Contract. The East Tennessee Materials and Energy Corporation (M and EC); a wholly owned subsidiary of Perma-Fix Environmental Services, Inc. (PESI), is a small business team member to CHPRC. Our scope includes project management; operation and maintenance of on-site storage, repackaging, treatment, and disposal facilities; and on-site waste management including waste receipt from generators and delivery to on-site and off-site treatment, storage, and disposal facilities. As part of this scope, M and EC staffs the centralized Waste Support Services organization responsible for all waste characterization and acceptance required to support CHPRC and waste generators across the Hanford Site. At the time of the CHPRC contract award (August 2008) slightly more than 9,000 cubic meters (m{sup 3}) of legacy waste was defined as 'no-path-forward waste'. A significant portion of this waste (7,650 m{sup 3}) comprised wastes with up to 50 grams of special nuclear materials (SNM) in oversized packages recovered during retrieval operations and large glove boxes removed from the Plutonium Finishing Plant (PFP). Through a collaborative effort between the DOE, CHPRC, and Perma-Fix Environmental Services, Inc. (PESI), pathways for these problematic wastes were developed that took advantage of commercial treatment capabilities at a nearby vendor facility, Perma-Fix Northwest (PFNW). In the spring of 2009, CHPRC initiated a pilot program under which they began shipping large package, low gram suspect TRU (<15 g SNM per container), and large package contact and remote handled MLLW to the off-site PFNW facility for treatment. PFNW is restricted by the SNM limits set for the total quantity of SNM allowed at the

Submillimeter laboratory identification of CH{sup +} and CH{sub 2}D{sup +}

Energy Technology Data Exchange (ETDEWEB)

Amano, T. [Department of Chemistry and Department of Physics and Astronomy, University of Waterloo, Waterloo, ON N2L 3G1 (Canada)

2015-01-22

Laboratory identification of two basic and important interstellar molecular ions is presented. The J = 1 - 0 rotational transition of {sup 12}CH{sup +} together with those of {sup 13}CH{sup +} and {sup 12}CD{sup +} was observed in the laboratory. The newly obtained frequencies were found to be different from those reported previously. Various experimental evidences firmly support the new measurements. In addition, the Zeeman effect and the spin-rotation hyperfine interaction enforce the laboratory identification with no ambiguity. Rotational lines of CH{sub 2}D{sup +} were observed in the submillimeter-wave region. This laboratory observation is consistent with a recent tentative identification of CH{sub 2}D{sup +} toward Ori IRc2.

Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)

NARCIS (Netherlands)

Koten, G. van; Beek, J.A.M. van; Dekker, G.P.C.M.; Wissing, E.; Zoutberg, M.C.; Stam, C.H.

1990-01-01

Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by

IMPLEMENTASI SANDI HILL UNTUK PENYANDIAN CITRA

Directory of Open Access Journals (Sweden)

JJ Siang

2002-01-01

Full Text Available Hill's code is one of text encoding technique. In this research, Hill's code is extended to image encoding. The image used is BMP 24 bit format. 2x2 and 3x3 matrices is used as a key. The results show that Hill's code is suitable for image whose RGB values vary highly. On the contrary, it is not suitable for less varied RGB images since its original pattern is still persisted in encrypted image. Hill's code for image encoding has also disadvantage in the case that the key matrix is not unique. However, for daily application, with good key matrix, Hill's code can be applied to encode image since it's process only deals with simple matrix operation so it become fast. Abstract in Bahasa Indonesia : Sandi Hill merupakan salah satu teknik penyandian teks. Dalam penelitian ini, pemakaian sandi Hill diperluas dari teks ke citra bertipe BMP 24 bit. Matriks yang dipakai berordo 2x2 dan 3x3. Hasil percobaan menunjukkan bahwa sandi Hill cocok untuk enkripsi citra dengan variasi nilai RGB antar piksel berdekatan yang tinggi (seperti foto, tapi tidak cocok untuk citra dengan variasi nilai RGB yang rendah (seperti gambar kartun karena pola citra asli masih tampak dalam citra sandi. Sandi Hill juga memiliki kelemahan dalam hal tidak tunggalnya matriks kunci yang dapat dipakai. Akan tetapi untuk pemakaian biasa, dengan pemilihan matriks kunci yang baik, sandi Hill dapat dipakai untuk penyandian karena hanya melibatkan operasi matriks biasa sehingga prosesnya relatif cepat. Kata kunci: Sandi Hill, Citra, Relatif Prima.

CH2 molecular beam source

International Nuclear Information System (INIS)

Porter, R.A.R.; Grosser, A.E.

1980-01-01

A molecular beam source of CH 2 is described. Coaxial beams of methylene halide and alkali metal react and the mixture is formed into a molecular beam. Passage through a mechanical velocity selector rotating at a suitably high speed purifies the beam, separating light, fast CH 2 from heavier, slower contaminating species

Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance.

Science.gov (United States)

Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo

2018-02-20

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

Posouzení vlivu nestandardních přítokových proudových poměrů na Q/h charakteristiku ostrohranného přelivu s obdélníkovým výřezem

OpenAIRE

Šmidrkalová, Nina

2012-01-01

Tato diplomová práce se zabývá problematikou měřících systémů, především užívajících metody Q/H charakteristiky. Popisuje ostrohranné přelivy a zmiňuje se i o měrných žlabech. Uvádí možnosti monitorování průtoků v napevno nainstalovaných profilech s volnou hladinou. Součástí práce je i experiment, který je zaměřen na simulaci nestandardních přítokových proudových poměrů před instalovaným přelivem pro stanovení jejich vlivu na Q/H charakteristiku. Experiment je proveden na pravoúhlém ostrohran...

Characterization of Vadose Zone Sediment: Slant Borehole SX-108 in the S-SX Waste Management Area

International Nuclear Information System (INIS)

Serne, R. Jeffrey; Last, George V.; Schaef, Herbert T.; Lanigan, David C.; Lindenmeier, Clark W.; Ainsworth, Calvin C.; Clayton, Ray E.; Legore, Virginia L.; O'Hara, Matthew J.; Brown, Christopher F.; Orr, Robert D.; Kutnyakov, Igor V.; Wilson, Teresa C.; Wagnon, Kenneth B.; Williams, Bruce A.; Burke, Deborah S.

2008-01-01

This report was revised in September 2008 to remove acid-extractable sodium data from Table 4.17. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is the fourth in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from a slant borehole installed beneath tank SX-108 (or simply SX-108 slant borehole)

Characterization of Vadose Zone Sediment: Borehole 299-W23-19 [SX-115] in the S-SX Waste Management Area

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Lanigan, David C.; Gee, Glendon W.; Lindenmeier, Clark W.; Clayton, Ray E.; Legore, Virginia L.; O' Hara, Matthew J.; Brown, Christopher F.; Last, George V.; Kutnyakov, Igor V.; Burke, Deborah S.; Wilson, Teresa C.; Williams, Bruce A.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.15 and 4.19. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The Tank Farm Vadose Zone Project is led by CH2M HILL Hanford Group, Inc. Their goals include defining risks from past and future single-shell tank farm activities, identifying and evaluating the efficacy of interim measures, and collecting geotechnical information and data. The purpose of these activities is to support future decisions made by the U.S. Department of Energy (DOE) regarding near-term operations, future waste retrieval, and final closure activities for the single-shell tank Waste Management Areas. To help in this effort, CH2M HILL Hanford Group, Inc. contracted with scientists at Pacific Northwest National Laboratory to analyze sediment samples collected from borehole 299-W23-19.

Characterization of Vadose Zone Sediment: Borehole 41-09-39 in the S-SX Waste Management Area

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Last, George V.; Schaef, Herbert T.; Lanigan, David C.; Lindenmeier, Clark W.; Ainsworth, Calvin C.; Clayton, Ray E.; Legore, Virginia L.; O' Hara, Matthew J.; Brown, Christopher F.; Orr, Robert D.; Kutnyakov, Igor V.; Wilson, Teresa C.; Wagnon, Kenneth B.; Williams, Bruce A.; Burke, Deborah S.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Table 5.15. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from borehole 41-09-39 installed adjacent to tank SX-109.

Characterization of Vadose Zone Sediment: Slant Borehole SX-108 in the S-SX Waste Management Area

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Last, George V.; Schaef, Herbert T.; Lanigan, David C.; Lindenmeier, Clark W.; Ainsworth, Calvin C.; Clayton, Ray E.; Legore, Virginia L.; O' Hara, Matthew J.; Brown, Christopher F.; Orr, Robert D.; Kutnyakov, Igor V.; Wilson, Teresa C.; Wagnon, Kenneth B.; Williams, Bruce A.; Burke, Deborah S.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Table 4.17. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is the fourth in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from a slant borehole installed beneath tank SX-108 (or simply SX-108 slant borehole).

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

International Nuclear Information System (INIS)

Chen Qi; Dai Wei; Tao Xumei; Yu Hui; Dai Xiaoyan; Yin Yongxiang

2006-01-01

A novel plasma atmospheric pressure abnormal glow discharge was used to investigate synthesis gas production from reforming methane and carbon dioxide. Special attentions were paid to the discharge characteristics and CH 4 , CO 2 conversion, H 2 , CO selectivity, and ratio of H 2 /CO varied with the changing of discharging power, the total flux, and the ratio of CH 4 /CO 2 . Experiments were performed in wider operation variables, the discharging power of 240 to 600 W, the CH 4 /CO 2 of 0.2 to 1.0 and the total flux of 140 to 500 mL/min. The experiments showed that the conversion of CH 4 and CO 2 was up to 91.9% and 83.2%, the selectivity of CO and H 2 was also up to 80% and 90% and H 2 /CO mole ratio was 0.2 to 1.2, respectively. A brief analysis for discharge characteristics and the experimental results were given

Mesoscopic CH 3 NH 3 PbI 3 /TiO 2 Heterojunction Solar Cells

KAUST Repository

Etgar, Lioz

2012-10-24

We report for the first time on a hole conductor-free mesoscopic methylammonium lead iodide (CH 3NH 3PbI 3) perovskite/TiO 2 heterojunction solar cell, produced by deposition of perovskite nanoparticles from a solution of CH 3NH 3I and PbI 2 in γ-butyrolactone on a 400 nm thick film of TiO 2 (anatase) nanosheets exposing (001) facets. A gold film was evaporated on top of the CH 3NH 3PbI 3 as a back contact. Importantly, the CH 3NH 3PbI 3 nanoparticles assume here simultaneously the roles of both light harvester and hole conductor, rendering superfluous the use of an additional hole transporting material. The simple mesoscopic CH 3NH 3PbI 3/TiO 2 heterojunction solar cell shows impressive photovoltaic performance, with short-circuit photocurrent J sc= 16.1 mA/cm 2, open-circuit photovoltage V oc = 0.631 V, and a fill factor FF = 0.57, corresponding to a light to electric power conversion efficiency (PCE) of 5.5% under standard AM 1.5 solar light of 1000 W/m 2 intensity. At a lower light intensity of 100W/m 2, a PCE of 7.3% was measured. The advent of such simple solution-processed mesoscopic heterojunction solar cells paves the way to realize low-cost, high-efficiency solar cells. © 2012 American Chemical Society.

Stanovení vybraných vonných látek v kosmetických prostředcích

OpenAIRE

Novotná, Petra

2011-01-01

Tato diplomová práce se zabývá stanovením vybraných vonných látek v kosmetických prostředcích. Úvodem je popsán výskyt, metody získávání a využití těchto látek. Jsou nepostradatelnou součástí především kosmetických výrobků, avšak u citlivých jedinců mohou vyvolat alergickou reakci. O příčinách vzniku a průběhu těchto nežádoucích projevů je v teoretické části také pojednáno. Je známo několik stovek až tisíc vonných látek používaných v parfumérském průmyslu, z nichž je 26 ustanoveno evropskými ...

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

International Nuclear Information System (INIS)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Schaef, Herbert T.; Williams, Bruce A.; Lanigan, David C.; Horton, Duane G.; Clayton, Ray E.; Mitroshkov, Alexandre V.; Legore, Virginia L.; O'Hara, Matthew J.; Brown, Christopher F.; Parker, Kent E.; Kutnyakov, Igor V.; Serne, Jennifer N.; Last, George V.; Smith, Steven C.; Lindenmeier, Clark W.; Zachara, John M.; Burke, Deborah Sd.

2001-01-01

The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is the first in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from RCRA borehole bore samples and composite samples. Intact cores from two RCRA boreholes (299-W22-48 and 299-W22-50) near the SX Tank Farm and four, large-quantity grab samples from outcrop sediment on and off the Hanford Site were sampled to better understand the fate of contaminants in the vadose zone beneath underground storage tanks at the Hanford Site. Borehole and outcrop samples analyzed for this report are located outside the tank farms, and therefore may be considered standard or background samples from which to compare contaminated sediments within the tank farms themselves. This report presents our interpretation of the physical, chemical, and mineralogical properties of the uncontaminated vadose zone sediments, and variations in the vertical distribution of these properties. The information presented in this report is intended to support preparation of the S-SX Field Investigation Report to be prepared by CH2M Hill Hanford Group, Inc. as well as future remediation actions at the S-SX Tank Farm

Aplikace legislativních norem u pojišťovacího zprostředkovatele OK GROUP

OpenAIRE

Kubiš, Michal

2015-01-01

Tato bakalářská práce se zabývá analýzou činností, vedoucích k bezproblémovému chodu společnosti OK GROUP a.s. v návaznosti na kontrolní činnost České národní banky. Analyzuje a podrobně popisuje kontrolní činnost jako takovou. V praktické části se zaměřím na sestavení návrhu vnitropodnikových směrnic pro zákonné fungování této firmy. This bachelor´s thesis deals with analysis of activities, which is going streight trought the smooth run of this in surance broker company OK GROUP a.s. in c...

Characterization of Vadose Zone Sediment: Borehole 299-E33-46 Near B 110 in the B BX-BY Waste Management Area

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Gee, Glendon W.; Schaef, Herbert T.; Lanigan, David C.; mccain, r. G.; Lindenmeier, Clark W.; Orr, Robert D.; Legore, Virginia L.; Clayton, Ray E.; Lindberg, Michael J.; Kutynakov, I. V.; Baum, Steven R.; Geiszler, Keith N.; Valenta, Michelle M.; Vickerman, Tanya S.; Royack, Lisa J.

2008-09-11

This report was revised in September 2008 to remove acid-ectractable sodium data from Table 4.17. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in December 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the B-BX-BY Waste Management Area. This report is the third in a series of three reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from a borehole installed approximately 4.5 m (15 ft) northeast of tank B- 110 (borehole 299-E33-46).

4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF-CH=CH-Py) radical cation salts containing poly(beta-diketonate) rare earth complexes: synthesis, crystal structure, photoluminescent and magnetic properties.

Science.gov (United States)

Pointillart, Fabrice; Maury, Olivier; Le Gal, Yann; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

2009-08-03

The reactions between the redox-active 4-(2-tetrathiafulvalenyl-ethenyl)pyridine ligand (TTF-CH=CH-Py) and the tris(1,1,1,5,5,5-hexafluoroacetylacetonate)Ln(III) (Ln = La and Nd) lead to the formation of compounds with the formulas {[La(hfac)(5)][(TTF-CH=CH-Py(*+))](2)} (1), {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2) (2), and {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2)(H(2)O)(C(6)H(14))(0.5) (3) (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion). These compounds have been characterized by single-crystal X-ray diffraction, optical, and magnetic measurements. Compounds 1, 2, and 3 crystallize in the monoclinic C2/c, triclinic P1, and monoclinic P2(1)/c space groups, respectively. La(III) adopts a tetradecahedral geometry, while Nd(III) stands in a distorted capped square antiprism one. In 1, the inorganic network is formed by the [La(hfac)(5)](2-) dianionic complexes, while it is formed by a pseudo-dimeric dianionic unit of formula {[Nd(hfac)(4)(H(2)O)](2)}(2-) in 2 and 3. In all crystal structures, the organic network is constituted by the TTF-CH=CH-Py(*+) radical cations. The inorganic and organic networks interact through intermolecular contacts between the pyridine moieties of the TTF-CH=CH-Py(*+) radical cations and the Ln(III) ions. The luminescence properties of the Nd(III) ions (9400 cm(-1)) and fluorescence band of the TTF-CH=CH-Py(*+) radical cations (10200 cm(-1)) have been observed and studied for compound 2. Complexes 2 and 3 are paramagnetic because of Nd(III) ions. Compound 2 is a paramagnetic luminescent TTF-radical-cation-based material. Resistivity measurements have also been performed on these materials.

Effect of permafrost thaw on CO2 and CH4 exchange in a western Alaska peatland chronosequence

International Nuclear Information System (INIS)

Johnston, Carmel E; Ewing, Stephanie A; Harden, Jennifer W; Fuller, Christopher C; Manies, Kristen; Varner, Ruth K; Wickland, Kimberly P; Koch, Joshua C; Jorgenson, M Torre

2014-01-01

Permafrost soils store over half of global soil carbon (C), and northern frozen peatlands store about 10% of global permafrost C. With thaw, inundation of high latitude lowland peatlands typically increases the surface-atmosphere flux of methane (CH 4 ), a potent greenhouse gas. To examine the effects of lowland permafrost thaw over millennial timescales, we measured carbon dioxide (CO 2 ) and CH 4 exchange along sites that constitute a ∼1000 yr thaw chronosequence of thermokarst collapse bogs and adjacent fen locations at Innoko Flats Wildlife Refuge in western Alaska. Peak CH 4 exchange in July (123 ± 71 mg CH 4 –C m −2 d −1 ) was observed in features that have been thawed for 30 to 70 (<100) yr, where soils were warmer than at more recently thawed sites (14 to 21 yr; emitting 1.37 ± 0.67 mg CH 4 –C m −2 d −1 in July) and had shallower water tables than at older sites (200 to 1400 yr; emitting 6.55 ± 2.23 mg CH 4 –C m −2 d −1 in July). Carbon lost via CH 4 efflux during the growing season at these intermediate age sites was 8% of uptake by net ecosystem exchange. Our results provide evidence that CH 4 emissions following lowland permafrost thaw are enhanced over decadal time scales, but limited over millennia. Over larger spatial scales, adjacent fen systems may contribute sustained CH 4 emission, CO 2 uptake, and DOC export. We argue that over timescales of decades to centuries, thaw features in high-latitude lowland peatlands, particularly those developed on poorly drained mineral substrates, are a key locus of elevated CH 4 emission to the atmosphere that must be considered for a complete understanding of high latitude CH 4 dynamics. (paper)

Silicon nitride and silicon etching by CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams

Energy Technology Data Exchange (ETDEWEB)

Kaler, Sanbir S.; Lou, Qiaowei; Donnelly, Vincent M., E-mail: vmdonnelly@uh.edu; Economou, Demetre J., E-mail: economou@uh.edu [Department of Chemical and Biomolecular Engineering, Plasma Processing Laboratory, University of Houston, Houston, Texas 77204 (United States)

2016-07-15

Silicon nitride (SiN, where Si:N ≠ 1:1) films low pressure-chemical vapor deposited on Si substrates, Si films on Ge on Si substrates, and p-Si samples were exposed to plasma beams emanating from CH{sub 3}F/O{sub 2} or CH{sub 3}F/CO{sub 2} inductively coupled plasmas. Conditions within the plasma beam source were maintained at power of 300 W (1.9 W/cm{sup 3}), pressure of 10 mTorr, and total gas flow rate of 10 sccm. X-ray photoelectron spectroscopy was used to determine the thicknesses of Si/Ge in addition to hydrofluorocarbon polymer films formed at low %O{sub 2} or %CO{sub 2} addition on p-Si and SiN. Polymer film thickness decreased sharply as a function of increasing %O{sub 2} or %CO{sub 2} addition and dropped to monolayer thickness above the transition point (∼48% O{sub 2} or ∼75% CO{sub 2}) at which the polymer etchants (O and F) number densities in the plasma increased abruptly. The C(1s) spectra for the polymer films deposited on p-Si substrates appeared similar to those on SiN. Spectroscopic ellipsometry was used to measure the thickness of SiN films etched using the CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams. SiN etching rates peaked near 50% O{sub 2} addition and 73% CO{sub 2} addition. Faster etching rates were measured in CH{sub 3}F/CO{sub 2} than CH{sub 3}F/O{sub 2} plasmas above 70% O{sub 2} or CO{sub 2} addition. The etching of Si stopped after a loss of ∼3 nm, regardless of beam exposure time and %O{sub 2} or %CO{sub 2} addition, apparently due to plasma assisted oxidation of Si. An additional GeO{sub x}F{sub y} peak was observed at 32.5 eV in the Ge(3d) region, suggesting deep penetration of F into Si, under the conditions investigated.

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, ReO{sub 3}(CH{sub 3}SO{sub 3}), VO(CH{sub 3}SO{sub 3}){sub 2}, and V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 4} and their thermal decomposition under N{sub 2} and O{sub 2} atmosphere

Energy Technology Data Exchange (ETDEWEB)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S. [Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry (Germany)

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO{sub 3}, UO{sub 2}(CH{sub 3}COO){sub 2}.2 H{sub 2}O, Re{sub 2}O{sub 7}(H{sub 2}O){sub 2}, and V{sub 2}O{sub 5} with CH{sub 3}SO{sub 3}H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm{sup 3}, Z=8) contains [MoO{sub 2}] moieties connected by [CH{sub 3}SO{sub 3}] ions to form layers parallel to (100). UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) {sup circle}, V=1.8937(3) nm{sup 3}, Z=8) consists of linear UO{sub 2}{sup 2+} ions coordinated by five [CH{sub 3}SO{sub 3}] ions, forming a layer structure. VO(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) {sup circle}, V=0.8290(2) nm{sup 3}, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO{sub 3}(CH{sub 3}SO{sub 3}) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) {sup circle}, V=1.1523(4) nm{sup 3}, Z=8) a chain structure exhibiting infinite O-[ReO{sub 2}]-O-[ReO{sub 2}]-O chains is formed. Each [ReO{sub 2}]-O-[ReO{sub 2}] unit is coordinated by two bidentate [CH{sub 3}SO{sub 3}] ions. V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 4} (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm{sup 3}, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH{sub 3}SO{sub 3}] ligands. Additional methanesulfonate ions connect the [V{sub 2}O{sub 3}] groups along [001]. Thermal decomposition of the compounds was monitored under N{sub 2} and O{sub 2} atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N{sub 2} the decomposition proceeds

Synthesis and Structural Characterisation of [Ir4(CO8(CH3(m4-h3-Ph2PCCPh(m-PPh2] and of the Carbonylation Product [Ir4(CO8{C(OCH3}(m4-h3-Ph2PCCPh(m-PPh2]; First Evidence for the Formation of a CO Cluster Adduct before CO Insertion

Directory of Open Access Journals (Sweden)

Braga Dario

1999-01-01

Full Text Available Deprotonation of [(mu-HIr4(CO10(mu-PPh2], 1, gives [Ir4(CO10(mu-PPh2]- that reacts with Ph2PCCPh and CH3I to afford [Ir4(CO8(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2], 2 (34%, besides [Ir4(CO9(mu3-eta³-Ph2PC(HCPh(mu-PPh2] and [(mu-HIr4(CO9(Ph2PCºCPh(mu-PPh2]. Compound 2 was characterised by a single crystal X-ray diffraction analysis and exhibits a flat butterfly of metal atoms, with the Ph2PCCPh ligand interacting with all four Ir atoms and the methyl group bonded terminally to a wingtip Ir atom. Carbonylation of 2 yields initially (25 °C, 20 min a CO addition product that, according to VT 31P{¹H} and 13C{¹H} studies, exists in solution in the form of two isomers 4A and 4B (8:1, and then (40 °C, 7 h, the CO insertion product [Ir4(CO8{C(OCH3}(mu4-eta³-Ph2PCCPh(mu-PPh2], 5. The molecular structure of 5, established by an X-ray analysis, is similar to that of 2, except for the acyl group that remains bound to the same Ir atom. The process is reversible at both stages. Treatment of 2 with PPh3 and P(OMe3 affords the CO substitution products [Ir4(CO7L(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2] (L = PPh3, 6 and P(OMe3, 7, instead of the expected CO inserted products. According to the ¹H and 31P{¹H} NMR studies, the PPh3 derivative 6 exists in the form of two isomers (1:1 that differ with respect to the position of this ligand.

SYNTHESIS OF NEW BIS(CYCLOPENTADIENYL)YTTRIUM COMPLEXES WITH ETHER FUNCTIONALIZED CYCLOPENTADIENYL LIGANDS - CRYSTAL-STRUCTURE OF [(C(5)H(4)CH(2)CH(2)OME)(2)Y(MU-H)(2)BH2

NARCIS (Netherlands)

LASKE, DA; DUCHATEAU, R; TEUBEN, JH; SPEK, AL

1993-01-01

Treatment of C(5)H(4)CH(2)CH(2)OMe.Li(TMEDA) (TMEDA = N, N, N', N' tetramethylethylenediamine) with half an equivalent of YCl3(THF)(3.5) in toluene afforded the salt- and solvent-free dimeric biscyclopentadienyl yttrium chloride [(C(5)H(4)CH(2)CH(2)OMe)(2)Y-(mu-Cl)](2) (1). Reaction of 1 with one

CH2 - Lighting and Physiology

Directory of Open Access Journals (Sweden)

Sergio Altomonte

2012-11-01

Full Text Available This paper explains the designed performances of the new CH2 building in Melbourne, Australia. CH2 is an environmentally significant project that involves biomimicry of natural systems to produce indoor conditions that are conducive to user comfort, health and productivity. This paper focuses on lighting and physiology and examines the solutions chosen for artificial and natural lighting and the likely effects these will have on building occupants. The purpose of the paper is to critically comment on the adopted strategy and, cognisance of contemporary thinking in lighting design, to judge the effectiveness of this aspect of the project with a view to later verification and post-occupancy review. The paper concludes that CH2 is an exemplar of lighting innovation that provides valuable lessons to designers of office buildings, particularly in the Melbourne CSD.

Enhancing Natural Attenuation through Bioaugmentation with Aerobic Bacteria that Degrade cis-1,2-Dichloroethene

Science.gov (United States)

2010-01-01

Studies with Site Groundwater ............................................................ 25  5.2.2  Titration Studies...Figure 4-4: Potentiometric Map of the Columbia Aquifer Figure 4-5: Shallow Groundwater TCE Plume Figure 4-6: Shallow Groundwater cDCE Plume Figure 4-7...west. Shallow groundwater typically ranges from 2 to 7 ft below ground surface (bgs) (CH2M HILL, 2008). A potentiometric map for the Columbia

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

Science.gov (United States)

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

Hodnocení elektrochemických charakteristik tvářených hořčíkových slitin typu Mg-Al-Zn

OpenAIRE

Slouková, Karolína

2016-01-01

Cílem této diplomové práce je zhodnotit elektrochemické charakteristiky slitin hořčíku. Teoretická část se zabývá popisem vlastností hořčíku i jeho slitin a také jejich korozních charakteristik. V experimentální části jsou interpretovány výsledky měření korozní odolnosti dvou tvářených hořčíkových slitin. Jednalo se o slitiny AZ31 a AZ61, které byly podrobeny měření v Hankových roztocích s přídavkem iontů Ca2+ a Mg2+ (SBF+) a bez jejich přídavku (SBF). Teplota roztoku během měření byla zvolen...

Constraining the Molecular Complexity in the Interstellar Medium—The Formation of Ethyl Methyl Ether (CH3OCH2CH3) in Star-forming Regions

Science.gov (United States)

Bergantini, Alexandre; Frigge, Robert; Kaiser, Ralf I.

2018-05-01

We report the first confirmed synthesis of ethyl methyl ether (EME, CH3CH2OCH3) within astrophysical model ices containing water (H2O) and methane (CH4) exposed to ionizing radiation at ultra-low temperatures of 5 K. EME (also known as methoxyethane), was recently observed toward Orion KL and currently is the largest confirmed oxygen-bearing molecule found in the interstellar medium. Exploiting isomer-selective photoionization (PI) of the subliming molecules in the temperature-programmed desorption phase at 10.49, 9.92, and 9.70 eV, coupled with reflectron time-of-flight mass spectrometry and isotopic substitution experiments (H2 18O–CH4), the detection of fragment ions of EME at m/z = 45 (C2H5O+) and m/z = 59 (C3H7O+), and probing the proton transfer in subliming ethanol–EME complexes via m/z = 61 (C3H9O+), the present study reveals that EME can be formed from suprathermal reactions initiated by cosmic rays and secondary electrons generated within astrophysical ices. The detection of EME in our experiments represents a significant advance in the understanding of formation pathways of complex organic molecules present in hot cores and helps to constrain astrochemical models on the formation of such species within molecular clouds.

Simulasi Numeris Karakteristik Pembakaran CH4/CO2/Udara dan CH4/CO2/O2 pada Counterflow Premixed Burner

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Hangga Wicaksono

2017-08-01

Full Text Available The high amount of CO2 produced in a conventional biogas reactor needs to be considered. A further analysis is needed in order to investigate the effect of CO2 addition especially in thermal and chemical kinetics aspect. This numerical study has been held to analyze the effect of CO2 in CH4/CO2/O­2 and CH4/CO2/Air premixed combustion. In this study one dimensional analisys in a counterflow burner has been performed. The volume fraction of CO2 used in this study was 0%-40% from CH4’s volume fraction, according to the amount of CO2 in general phenomenon. Based on the flammability limits data, the volume fraction of CH4 used was 5-61% in O2 environment and 5-15% in air environment. The results showed a decreasing temperature along with the increasing percentage of CO2 in each mixtures, but the effect was quite smaller especially in stoichiometric and lean mixture. CO2 could affects thermally (by absorbing heat due to its high Cp and also made the production of unburnt fuel species such as CO relatively higher.

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO2 and CH4 Exchange Responds to Changes in Temperature and Precipitation

Science.gov (United States)

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; Arora, B.; Torn, M. S.

2017-12-01

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO2 and CH4 exchange. Here we test hypotheses in ecosys for topographic controls on CO2 and CH4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO2 influxes and CH4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) than in higher (rims) within LCPs and FCPs. Spatially aggregated CO2 and CH4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52-56 g C m-2 yr-1) and CH4 sources (4-6 g C m-2 yr-1), and higher features as near C neutral (-2-15 g C m-2 yr-1) and CH4 neutral (0.0-0.1 g C m-2 yr-1). Much of the spatial and temporal variations in CO2 and CH4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.

Geographic Information Systems in Developing Countries – What are the Ethical Issues we need to be aware of ? / Geografické Informační Systémy A Jejich Využití V Rozvojových Zemích - Jakým Etickým Otázkám Musíme Čelit?

Directory of Open Access Journals (Sweden)

Pánek Jiří

2013-06-01

Full Text Available Využití geografických informačních systémů (GIS v rozvojových zemích se musí potýkat s historickou skepsí, kterou mapy, jako nástroj moci, mají mezi původními obyvateli. Participativní přístupy v mapování a GIS se snaží přistupovat k místním prostorovým znalostem s větší mírou společenské a etické zodpovědnosti. Článek se soustředí na popis vybraných důvodů, které vedly ke skeptickému postoji vůči GIS, a na identifikaci základních etických otázek sběru a interpretace prostorových informací v rozvojových zemích na příkladu mapování vodních zdrojů ve vesnici Koffiekraal v Jihoafrické republice.

[(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Medeiros, David R

2003-03-10

The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

Technical Baseline Summary Description for the Tank Farm Contractor

International Nuclear Information System (INIS)

TEDESCHI, A.R.

2000-01-01

This document is a revision of the document titled above, summarizing the technical baseline of the Tank Farm Contractor. It is one of several documents prepared by CH2M HILL Hanford Group, Inc. to support the U.S. Department of Energy Office of River Protection Tank Waste Retrieval and Disposal Mission at Hanford

Pulsed CH3OH terahertz laser radiation pumped by 9P(36) CO2 lasers

International Nuclear Information System (INIS)

Jiu Zhixian; Zuo Duluo; Miao Liang; Cheng Zuhai

2011-01-01

An efficient pulsed CH 3 OH terahertz (THz) laser pumped by a TEA CO 2 laser was investigated experimentally. A simple terahertz cavity and a TEA CO 2 laser for the optically pumped THz radiation were studied experimentally. To improve THz laser energy and photon conversion efficiency, two different TEA CO 2 lasers were developed to pump CH 3 OH. When CH 3 OH was pumped by the 9P(36) line with different powers of the CO 2 laser, the generation of terahertz radiation with energy as high as 0.307mJ and 23.75mJ were obtained, respectively. The corresponding photon conversion efficiencies were 0.29% and 2.4%. The photon conversion efficiency increases by a factor of about 8. Meanwhile, higher peak power of pump laser effectively improves the photon conversion efficiency. And the optimum THz laser pressure increases with narrower pulse width of pump laser because of increasing absorptive gases molecules of CH 3 OH with higher peak power of pump laser.

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

International Nuclear Information System (INIS)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Schaef, Herbert T.; Williams, Bruce A.; Lanigan, David C.; Horton, Duane G.; Clayton, Ray E.; Mitroshkov, Alexandre V.; Legore, Virginia L.; O'Hara, Matthew J.; Brown, Christopher F.; Parker, Kent E.; Kutnyakov, Igor V.; Serne, Jennifer N.; Last, George V.; Smith, Steven C.; Lindenmeier, Clark W.; Zachara, John M.; Burke, Deborah S.

2008-01-01

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Schaef, Herbert T.; Williams, Bruce A.; Lanigan, David C.; Horton, Duane G.; Clayton, Ray E.; Mitroshkov, Alexandre V.; Legore, Virginia L.; O' Hara, Matthew J.; Brown, Christopher F.; Parker, Kent E.; Kutnyakov, Igor V.; Serne, Jennifer N.; Last, George V.; Smith, Steven C.; Lindenmeier, Clark W.; Zachara, John M.; Burke, Deborah S.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples.

Measurements of the near-surface flow over a hill

Science.gov (United States)

Vosper, S. B.; Mobbs, S. D.; Gardiner, B. A.

2002-10-01

The near-surface flow over a hill with moderate slope and height comparable with the boundary-layer depth is investigated through field measurements of the mean flow (at 2 m), surface pressure, and turbulent momentum flux divergence between 8 and 15 m. The measurements were made along an east-west transect across the hill Tighvein (height 458 m, approximate width 8 km) on the Isle of Arran, south-west Scotland, during two separate periods, each of around three-weeks duration. Radiosonde ascents are used to determine the variation of a Froude number, FL = U/NL, where U is the wind speed at the middle-layer height, hm, N is the mean Brunt-Väisälä frequency below this height and L is a hill length-scale. Measurements show that for moderately stratified flows (for which FL 0.25) a minimum in the hill-induced surface-pressure perturbation occurs across the summit and this is accompanied by a maximum in the near-surface wind speed. In the more strongly stratified case (FL 0.25) the pressure field is more asymmetric and the lee-slope flow is generally stronger than on the windward slope. Such a flow pattern is qualitatively consistent with that predicted by stratified linear boundary-layer and gravity-wave theories. The near-surface momentum budget is analysed by evaluating the dominant terms in a Bernoulli equation suitable for turbulent flow. Measurements during periods of westerly flow are used to evaluate the dominant terms, and the equation is shown to hold to a reasonable approximation on the upwind slope of the hill and also on the downwind slope, away from the summit. Immediately downwind of the summit, however, the Bernoulli equation does not hold. Possible reasons for this, such as non-separated sheltering and flow separation, are discussed.

Braked rotation of CH3 group in L-alanine monocrystals: temperature transformation of EPR spectrum

International Nuclear Information System (INIS)

Lemanov, V.V.; Sochava, L.S.

2003-01-01

EPR spectra temperature transformation of the irradiated alanine crystals is used for studying rotation of CH 3 methyl group in L-alamine monocrystals. 60 Co (2 x 10 4 Gy dose) was applied as a γ-radiation source. The simple method of experimental data processing which is reduced to obtaining the resonance lines width dependence on the temperature is used for the quantitative analysis of the spectrum temperature transformation. Temperature dependence of the CH 3 group rotation frequency is identified on the basis of these data. Activation energy U = 0.18 eV and pre-exponential multiplier ω 0 = 10 13 s -1 are determined from the EPR spectra temperature transformation which are in good agreement with values obtained earlier from the measurements of the proton spin-lattice relaxation in alanine polycrystal samples [ru

Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

Science.gov (United States)

Zhou, Yong; Zhang, Dong H

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

Automated CO2, CH4 and N2O Fluxes from Tree Stems and Soils: Magnitudes, Temporal Patterns and Drivers

Science.gov (United States)

Barba, J.; Poyatos, R.; Vargas, R.

2017-12-01

The emissions of the main greenhouse gases (GHG; CO2, CH4 and N2O) through tree stems are still an uncertain component of the total GHG balance of forests. Despite that stem CO2 emissions have been studied for several decades, it is still unclear the drivers and spatiotemporal patterns of CH4 and N2O stem emissions. Additionally, it is unknown how stem emissions could be related to soil physiological processes or environmental conditions. We measured CO2, CH4 and N2O emissions hourly from April to July 2017 at two different heights (75 [LStem] and 150cm [HStem]) of bitternut hickory (Carya cordiformis) trees and adjacent soil locations in a forested area in the Mid Atlantic of the USA. We designed an automated system to continuously measure the three greenhouse gases (GHG) in stems and soils. Stem and soil CO2 emissions showed similar seasonal patterns with an average of 6.56±0.09 (soil), 3.72±0.05 (LStem) and 2.47±0.04 µmols m-2 s-1 (HStem) (mean±95% CI). Soil temperature controlled CO2 fluxes at both daily and seasonal scales (R2>0.5 for all cases), but there was no clear effect of soil moisture. The stems were a clear CH4 source with emissions decreasing with height (0.35±0.02 and 0.25±0.01 nmols m-2 s-1 for LStem and HStem, respectively) with no apparent seasonal pattern, and no clear relationship with environmental drivers (e.g., temperature, moisture). In contrast, soil was a CH4 sink throughout the experiment (-0.55±0.02 nmols m-2 s-1) and its seasonal pattern responded to moisture changes. Despite soil and stem N2O emissions did not show a seasonal pattern or apparent dependency on temperature or moisture, they showed net N2O emissions with a decrease in emissions with stem height (0.29±0.05 for soil, 0.38±0.06 for LStem and 0.28±0.05 nmols m-2 s-1 for HStem). The three GHG emissions decreased with stem height at similar rates (33%, 28% and 27% for CO2, CH4 and N2O, respectively). These results suggest that the gases were not produced in the stem

EFFECT OF DIFFERENT COOLING SYSTEMS ON LYING TIME OF DAIRY COWS IN CUBICLES WITH SEPARATED MANURE SOLIDS BEDDING VPLYV ROZDIELNYCH SYSTÉMOV OCHLADZOVANIA NA DOBU LEŢANIA DOJNÍC USTAJNENÝCH V LEŢISKOVÝCH BOXOCH PODSTIELANÝCH SEPAROVANÝM KALOM HNOJOVICE

Directory of Open Access Journals (Sweden)

Jana LENDELOVÁ

2012-12-01

Full Text Available The aim of this study was to investigate the changes of lying time and other behaviour manifestations of dairy cows during usage of different cooling systems of animals. Alternative hypothesis was presumption, that the lying time of cows in lying cubicles with applied two different cooling systems are indifferent. The sprinkling system was used to animal cooling in group S in summer time. In group SV was disposable sprinkling system and diagonally rotated ventilators. Activities and the rest of animals were evaluated in 10 minute intervals using a camera system for 24 hours. Data obtained was tested by nonparametric Kruskal-Wallis one-way ANOVA and multiple comparison test for detecting of significant differences in the behaviors between groups of cows. There was found positive effect of animal enhanced cooling using sprinkling system with increased air movement by ventilators. It reflected in significant prolongation of whole lying time and shortening of time, when animals were standing. It resulted from final values of investigated behaviour manifestations of dairy cattle within 24 hour period that animals in group SV with sprinklers and ventilators lay in stalls longer than in group S with sprinklers, but without ventilators (10.76 h*d-1*cow-1 vs. 7.71 h*d-1*cow-1, P<0.001. The total time spent by lying in stalls and in alley represented in group SV 11.31 h*d-1*cow-1, and in group S 10.22 h*d-1*cow-1. Animals, from group S without ventilators, which were less cooled, were significantly more lying down in alleys (2.52 h*d-1*cow-1 vs. 0.56 h*d-1*cow-1, P<0.001.Cieľom štúdie bolo skúmanie zmeny dĺţky leţania a ďalších prejavov správania dojníc pri pouţití rôznych spôsobov ochladzovania zvierat. Alternatívnou hypotézou bol predpoklad, ţe doba leţania dojníc v leţiskách s dvomi rozdielnymi spôsobmi ochladzovania nie je rovnaká. V letnom období bol k ochladzovaniu v skupine S vyuţívaný sprchový systém, v skupine SV

Bimolecular reaction of CH3 + CO in solid p-H2: Infrared absorption of acetyl radical (CH3CO) and CH3-CO complex

Science.gov (United States)

Das, Prasanta; Lee, Yuan-Pern

2014-06-01

We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm-1 were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm-1 appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm-1. The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol-1 and internal energy ˜42 kJ mol-1 upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ˜27 kJ mol-1 for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

On the use of satellite-derived CH4 : CO2 columns in a joint inversion of CH4 and CO2 fluxes

NARCIS (Netherlands)

Pandey, S.

2015-01-01

We present a method for assimilating total column CH4 : CO2 ratio measurements from satellites for inverse modeling of CH4 and CO2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH4 : CO2 are multiplied by model-derived total column CO2 and only the

Kinetics of the R + HBr ↔ RH + Br (CH3CHBr, CHBr2 or CDBr2) equilibrium. Thermochemistry of the CH3CHBr and CHBr2 radicals

International Nuclear Information System (INIS)

Seetula, Jorma A.; Eskola, Arkke J.

2008-01-01

The kinetics of the reaction of the CH 3 CHBr, CHBr 2 or CDBr 2 radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH 3 CHBr (or CHBr 2 or CDBr 2 ) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH 3 CHBr 2 (or CHBr 3 or CDBr 3 ). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH 3 CHBr + HBr) and from 288 to 477 K (CHBr 2 + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm 3 molecule -1 s -1 , no error limits for the third reaction): k(CH 3 CHBr + HBr) = (1.7 ± 1.2) x 10 -13 exp[+ (5.1 ± 1.9) kJ mol -1 /RT], k(CHBr 2 + HBr) = (2.5 ± 1.2) x 10 -13 exp[-(4.04 ± 1.14) kJ mol -1 /RT] and k(CDBr 2 + HBr) = 1.6 x 10 -13 exp(-2.1 kJ mol -1 /RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH 3 CHBr and CHBr 2 radicals and an experimental entropy value at 298 K for the CH 3 CHBr radical were obtained using a second-law method. The result for the entropy value for the CH 3 CHBr radical is 305 ± 9 J K -1 mol -1 . The results for the enthalpy of formation values at 298 K are (in kJ mol -1 ): 133.4 ± 3.4 (CH 3 CHBr) and 199.1 ± 2.7 (CHBr 2 ), and for α-C-H bond dissociation energies of analogous compounds are (in kJ mol -1 ): 415.0 ± 2.7 (CH 3 CH 2 Br) and 412.6 ± 2.7 (CH 2 Br 2 ), respectively

Unveiling the chemistry of interstellar CH. Spectroscopy of the 2 THz N = 2 ← 1 ground state line

Science.gov (United States)

Wiesemeyer, H.; Güsten, R.; Menten, K. M.; Durán, C. A.; Csengeri, T.; Jacob, A. M.; Simon, R.; Stutzki, J.; Wyrowski, F.

2018-04-01

Context. The methylidyne radical CH is commonly used as a proxy for molecular hydrogen in the cold, neutral phase of the interstellar medium. The optical spectroscopy of CH is limited by interstellar extinction, whereas far-infrared observations provide an integral view through the Galaxy. While the HF ground state absorption, another H2 proxy in diffuse gas, frequently suffers from saturation, CH remains transparent both in spiral-arm crossings and high-mass star forming regions, turning this light hydride into a universal surrogate for H2. However, in slow shocks and in regions dissipating turbulence its abundance is expected to be enhanced by an endothermic production path, and the idea of a "canonical" CH abundance needs to be addressed. Aim. The N = 2 ← 1 ground state transition of CH at λ149 μm has become accessible to high-resolution spectroscopy thanks to the German Receiver for Astronomy at Terahertz Frequencies (GREAT) aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Its unsaturated absorption and the absence of emission from the star forming regions makes it an ideal candidate for the determination of column densities with a minimum of assumptions. Here we present an analysis of four sightlines towards distant Galactic star forming regions, whose hot cores emit a strong far-infrared dust continuum serving as background signal. Moreover, if combined with the sub-millimeter line of CH at λ560 μm , environments forming massive stars can be analyzed. For this we present a case study on the "proto-Trapezium" cluster W3 IRS5. Methods: While we confirm the global correlation between the column densities of HF and those of CH, both in arm and interarm regions, clear signposts of an over-abundance of CH are observed towards lower densities. However, a significant correlation between the column densities of CH and HF remains. A characterization of the hot cores in the W3 IRS5 proto-cluster and its envelope demonstrates that the sub

EMG activities and plantar pressures during ski jumping take-off on three different sized hills.

Science.gov (United States)

Virmavirta, M; Perttunen, J; Komi, P V

2001-04-01

Different profiles of ski jumping hills have been assumed to make the initiation of take-off difficult especially when moving from one hill to another. Neuromuscular adaptation of ski jumpers to the different jumping hills was examined by measuring muscle activation and plantar pressure of the primary take-off muscles on three different sized hills. Two young ski jumpers volunteered as subjects and they performed several trials from each hill (K-35 m, K-65 m and K-90 m) with the same electromyographic (EMG) electrode and insole pressure transducer set-up. The results showed that the differences in plantar pressure and EMGs between the jumping hills were smaller than expected for both jumpers. The small changes in EMG amplitudes between the hills support the assumption that the take-off was performed with the same intensity on different jumping hills and the timing of the gluteus EMG demonstrates well the similarity of the muscle activation on different hills. On the basis of the results obtained it seems that ski jumping training on small hills does not disturb the movement patterns for bigger hills and can also be helpful for special take-off training with low speed.

Physical and Liquid Chemical Simulant Formulations for Transuranic Waste in Hanford Single-Shell Tanks

International Nuclear Information System (INIS)

Rassat, Scot D.; Bagaasen, Larry M.; Mahoney, Lenna A.; Russell, Renee L.; Caldwell, Dustin D.; Mendoza, Donaldo P.

2003-01-01

CH2M HILL Hanford Group, Inc. (CH2M HILL) is in the process of identifying and developing supplemental process technologies to accelerate the tank waste cleanup mission. A range of technologies is being evaluated to allow disposal of Hanford waste types, including transuranic (TRU) process wastes. Ten Hanford single-shell tanks (SSTs) have been identified whose contents may meet the criteria for designation as TRU waste: the B-200 series (241-B-201, -B-202, -B 203, and B 204), the T-200 series (241-T-201, T 202, -T-203, and -T-204), and Tanks 241-T-110 and -T-111. CH2M HILL has requested vendor proposals to develop a system to transfer and package the contact-handled TRU (CH-TRU) waste retrieved from the SSTs for subsequent disposal at the Waste Isolation Pilot Plant (WIPP). Current plans call for a modified ''dry'' retrieval process in which a liquid stream is used to help mobilize the waste for retrieval and transfer through lines and vessels. This retrieval approach requires that a significant portion of the liquid be removed from the mobilized waste sludge in a ''dewatering'' process such as centrifugation prior to transferring to waste packages in a form suitable for acceptance at WIPP. In support of CH2M HILL's effort to procure a TRU waste handling and packaging process, Pacific Northwest National Laboratory (PNNL) developed waste simulant formulations to be used in evaluating the vendor's system. For the SST CH-TRU wastes, the suite of simulants includes (1) nonradioactive chemical simulants of the liquid fraction of the waste, (2) physical simulants that reproduce the important dewatering properties of the waste, and (3) physical simulants that can be used to mimic important rheological properties of the waste at different points in the TRU waste handling and packaging process. To validate the simulant formulations, their measured properties were compared with the limited data for actual TRU waste samples. PNNL developed the final simulant formulations

N2O, NO and CH4 exchange, and microbial N turnover over a Mediterranean pine forest soil

Directory of Open Access Journals (Sweden)

P. Rosenkranz

2006-01-01

Full Text Available Trace gas exchange of N2O, NO/NO2 and CH4 between soil and the atmosphere was measured in a typical Mediterranean pine (Pinus pinaster forest during two intensive field campaigns in spring and autumn 2003. Furthermore, gross and net turnover rates of N mineralization and nitrification as well as soil profiles of N2O and CH4 concentrations were determined. For both seasons a weak but significant N2O uptake from the atmosphere into the soil was observed. During the unusually dry and hot spring mean N2O uptake was −4.32 µg N m-2 h-1, whereas during the wet and mild autumn mean N2O uptake was −7.85 µg N m-2 h-1. The observed N2O uptake into the soil was linked to the very low availability of inorganic nitrogen at the study site. Organic layer gross N mineralization decreased from 5.06 mg N kg-1 SDW d-1 in springtime to 2.68 mg N kg-1 SDW d-1 in autumn. Mean NO emission rates were significantly higher in springtime (9.94 µg N m-2 h-1 than in autumn (1.43 µg N m-2 h-1. A significant positive correlation between NO emission rates and gross N mineralization as well as nitrification rates was found. The negative correlation between NO emissions and soil moisture was explained with a stimulation of aerobic NO uptake under N limiting conditions. Since NO2 deposition was continuously higher than NO emission rates the examined forest soil functioned as a net NOx sink. Observed mean net CH4 uptake rates were in spring significantly higher (−73.34 µg C m-2 h-1 than in autumn (−59.67 µg C m-2 h-1. Changes in CH4 uptake rates were strongly negatively correlated with changes in soil moisture. The N2O and CH4 concentrations in different soil depths revealed the organic layer and the upper 0.1 m of mineral soil as the most important soil horizons for N2O and CH4 consumption.

Hanford Tank 241-C-106: Impact of Cement Reactions on Release of Contaminants from Residual Waste

International Nuclear Information System (INIS)

Deutsch, William J.; Krupka, Kenneth M.; Lindberg, Michael J.; Cantrell, Kirk J.; Brown, Christopher F.; Schaef, Herbert T.

2006-01-01

The CH2M HILL Hanford Group, Inc. (CH2M HILL) is producing risk/performance assessments to support the closure of single-shell tanks at the U.S. Department of Energy's Hanford Site. As part of this effort, staff at Pacific Northwest National Laboratory were asked to develop release models for contaminants of concern that are present in residual sludge remaining in tank 241-C-106 (C-106) after final retrieval of waste from the tank. Initial work to produce release models was conducted on residual tank sludge using pure water as the leaching agent. The results were reported in an earlier report. The decision has now been made to close the tanks after waste retrieval with a cementitious grout to minimize infiltration and maintain the physical integrity of the tanks. This report describes testing of the residual waste with a leaching solution that simulates the composition of water passing through the grout and contacting the residual waste at the bottom of the tank.

DEWATERING TREATMENT SCALE-UP TESTING RESULTS OF HANFORD TANK WASTES

International Nuclear Information System (INIS)

TEDESCHI AR

2008-01-01

This report documents CH2M HILL Hanford Group Inc. (CH2M HILL) 2007 dryer testing results in Richland, WA at the AMEC Nuclear Ltd., GeoMelt Division (AMEC) Horn Rapids Test Site. It provides a discussion of scope and results to qualify the dryer system as a viable unit-operation in the continuing evaluation of the bulk vitrification process. A 10,000 liter (L) dryer/mixer was tested for supplemental treatment of Hanford tank low-activity wastes, drying and mixing a simulated non-radioactive salt solution with glass forming minerals. Testing validated the full scale equipment for producing dried product similar to smaller scale tests, and qualified the dryer system for a subsequent integrated dryer/vitrification test using the same simulant and glass formers. The dryer system is planned for installation at the Hanford tank farms to dry/mix radioactive waste for final treatment evaluation of the supplemental bulk vitrification process

Making a Lasting Impression: Recovery Act Reporting At Hanford - 12528

Energy Technology Data Exchange (ETDEWEB)

Tebrugge, Kimberly; Disney, Maren [CH2MHILL Plateau Remediation Company, Richland, WA (United States)

2012-07-01

The award of American Recovery and Reinvestment Act funding came with an unprecedented request for transparency to showcase to the American public how the stimulus funding was being put to work to achieve the goals put forth by the U.S. Government. At the U.S. Department of Energy Hanford Site, this request manifested in a contract requirement to provide weekly narrative, photos and video to highlight Recovery Act-funded projects. For DOE contractor CH2M HILL Plateau Remediation Company (CH2M HILL), the largest recipient of Hanford's funding, the reporting mechanism evolved into a communications tool for documenting the highly technical cleanup, then effectively sharing that story with the DOE and its varying stakeholder audiences. The report set the groundwork for building a streaming narrative of week-by-week progress. With the end of the Recovery Act, CH2M HILL is applying lessons learned from this stringent, transparent reporting process to its long-term reporting and communications of the progress being made in nuclear decommissioning at Hanford. (authors)

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

Energy Technology Data Exchange (ETDEWEB)

Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States); Klippenstein, Stephen J. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.

Interannual variability in CO2 and CH4 exchange in a brackish tidal marsh in Northern California

Science.gov (United States)

Knox, S. H.; Windham-Myers, L.; Anderson, F. E.; Bergamaschi, B. A.

2017-12-01

Carbon (C) cycling in coastal wetlands is difficult to measure and model due to extremely dynamic atmospheric and hydrologic fluxes, as well as sensitivities to dynamic land- and ocean-based drivers. To date, few studies have begun continuous measurements of net ecosystem CO2 exchange (NEE) in these systems, and as such our understanding of the key drivers of NEE in coastal wetlands remain poorly understood. Recent eddy covariance measurements of NEE in these environments show considerable variability both within and across sites, with daily CO2 uptake and annual net CO2 budgets varying by nearly an order of magnitude between years and across locations. Furthermore, measurements of CH4 fluxes in these systems are even more limited, despite the potential for CH4 emissions from brackish and freshwater coastal wetlands. Here we present 3 years of near-continuous eddy covariance measurements of CO2 and CH4 fluxes from a brackish tidal marsh in Northern California and explore the drivers of interannual variability in CO2 and CH4 exchange. CO2 fluxes showed significant interannual variability; net CO2 uptake was near-zero in 2014 (6 ± 26 g C-CO2 m-2 yr-1), while much greater uptake was observed in 2015 and 2016 (209 ± 27 g C- CO2 m-2 yr-1 and 243 ± 26 g C-CO2 m-2 yr-1, respectively). Conversely, annual CH4 emissions were small and consistent across years, with the wetland emitting on average 1 ± 0.1 g C-CH4 m-2 yr-1. With respect to the net atmospheric GHG budget (assuming a sustained global warming potential (SGWP) of 45, expressed in units of CO2 equivalents), the wetland was near neutral in 2014, but a net GHG sink of 706 ± 105 g CO2 eq m-2 yr-1 and 836 ± 83 g CO2 eq m-2 yr-1 in 2015 and 2016, respectively. The large interannual variability in CO2 exchange was driven by notable year-to-year differences in temperature and precipitation as California experienced a severe drought and record high temperatures from 2012 to 2015. The large interannual variability in

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

Science.gov (United States)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-10 mmol m-2 d-1) were observed during the dry season. Close to the tributaries water inputs where the water column is well mixed, the average diffusive flux is 8 mmol m-2 d-1. CH4 ebullition was 3.5 mmol m-2 d-1 and no ebullition was observed for a water depth higher than 5m. The zone under the influence of the water inputs from tributaries represents 25% of the surface of the reservoir but contributed half of total CH4 emissions from the reservoir (29MgC month-1). Ebullition contributed only to 12% of total CH4 emissions over a year but it contributed up to 60% during the dry season. CH4 emissions from the Rio Grande Reservoir contributed 30% of the total GHG emissions (38GgCO2eq y-1). Overall, this study show that the majority of CH4 emissions from this

Summer fluxes of atmospheric greenhouse gases N{sub 2}O, CH{sub 4} and CO{sub 2} from mangrove soil in South China

Energy Technology Data Exchange (ETDEWEB)

Chen, G.C. [Department of Biology and Chemistry, City University of Hong Kong, Hong Kong SAR (China); Tam, N.F.Y., E-mail: bhntam@cityu.edu.hk [Department of Biology and Chemistry, City University of Hong Kong, Hong Kong SAR (China); Ye, Y. [State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen, Fujian (China)

2010-06-01

The atmospheric fluxes of N{sub 2}O, CH{sub 4} and CO{sub 2} from the soil in four mangrove swamps in Shenzhen and Hong Kong, South China were investigated in the summer of 2008. The fluxes ranged from 0.14 to 23.83 {mu}mol m{sup -2} h{sup -1}, 11.9 to 5168.6 {mu}mol m{sup -2} h{sup -1} and 0.69 to 20.56 mmol m{sup -2} h{sup -1} for N{sub 2}O, CH{sub 4} and CO{sub 2}, respectively. Futian mangrove swamp in Shenzhen had the highest greenhouse gas fluxes, followed by Mai Po mangrove in Hong Kong. Sha Kong Tsuen and Yung Shue O mangroves in Hong Kong had similar, low fluxes. The differences in both N{sub 2}O and CH{sub 4} fluxes among different tidal positions, the landward, seaward and bare mudflat, in each swamp were insignificant. The N{sub 2}O and CO{sub 2} fluxes were positively correlated with the soil organic carbon, total nitrogen, total phosphate, total iron and NH{sub 4}{sup +}-N contents, as well as the soil porosity. However, only soil NH{sub 4}{sup +}-N concentration had significant effects on CH{sub 4} fluxes.

Air-Sea Interactions of Natural Long-Lived Greenhouse Gases (CO2, N2O, CH4) in a Changing Climate

Digital Repository Service at National Institute of Oceanography (India)

Bakker, D.C.E.; Bange, H.W.; Gruber, N.; Johannessen, T.; Upstill-Goddard, R.C.; Borges, A.V.; Delille, B.; Loscher, C.R.; Naqvi, S.W.A.; Omar, A.M.; Santana-Casiano, J.M.

at m o sp h er ic li fe ti m es G as R o le in at m o sp h er ic ch em is tr y O ce an ic co n tr ib u ti o n to co n te m p o ra ry at m o sp h er ic b u d g et Im p ac t o f en v ir o n m en ta l ch an g e o n ai r- se a g as ex ch an g e in th e tw... en ty -fi rs t ce n tu ry G lo b al w ar m in g O ce an ac id ifi ca ti o n O p en o ce an d eo x y g en at io n C o as ta l eu tr o p h ic at io n an d h y p o x ia C O 2 In er t N et o ce an si n k fo r ab o u t 3 0 % o f C O 2 em is si o n s fr o m...

(Phosphinoalkyl)silanes. 4.(1) Hydrozirconation as a Non-Photochemical Route to (Phosphinopropyl)silanes: Facile Assembly of the Bis(3-(diphenylphosphino)propyl)silyl ("biPSi") Ligand Framework. Access to the Related Poly(3-(dimethylsilyl)propyl)phosphines R(n)()P(CH(2)CH(2)CH(2)SiMe(2)H)(3)(-)(n)() (n = 1, R = Ph; n = 0).

Science.gov (United States)

Zhou, Xiaobing; Stobart, Stephen R.; Gossage, Robert A.

1997-08-13

Treatment of SiEt(3)(CH=CH(2)) with ZrCp(2)HCl (Schwartz's reagent) followed by reaction with PPh(2)Cl provides a high-yield (75%) route to Ph(2)PCH(2)CH(2)SiEt(3), and accordingly hydrozirconation of CH(2)=CHCH(2)SiHMe(2) affords the intermediate ZrCp(2)(CH(2)CH(2)CH(2)SiHMe(2))Cl (2). The latter, which is very sensitive to hydrolysis and reacts with HCl forming SiHMe(2)Pr(n)() and with NBS or I(2) affording SiHMe(2)CH(2)CH(2)CH(2)X (X = Br (3), I (4)), behaves similarly with PPh(2)Cl, PPhCl(2), or PBr(3) undergoing cleavage to the known Ph(2)PCH(2)CH(2)CH(2)SiMe(2)H (i.e. chelH, A) and the novel bis- and tris(silylpropyl)phosphines PhP(CH(2)CH(2)CH(2)SiMe(2)H)(2) (5) and P(CH(2)CH(2)CH(2)SiMe(2)H)(3) (6), respectively, with concomitant formation of ZrCp(2)Cl(2). Corresponding hydroboration of allylsilanes is facile, but subsequent phosphine halide cleavage yields (phosphinoalkyl)silanes only as constituents of intractable mixtures. Hydrozirconation followed by phosphination with PPh(2)Cl also converts SiHMe(CH(2)CH=CH(2))(2) to SiHMe(CH(2)CH(2)CH(2)PPh(2))(2) (i.e. biPSiH, B) together with a propyl analogue Ph(2)PCH(2)CH(2)CH(2)SiMe(Pr(n)())H (7) of A (ca. 2:1 ratio), as well as SiH(CH(2)CH=CH(2))(3) to a mixture (ca. 5:2:1 ratio) of SiH(CH(2)CH(2)CH(2)PPh(2))(3) (i.e. triPSiH, C), a new analogue SiH(Pr(n)())(CH(2)CH(2)CH(2)PPh(2))(2) (8) of B, and a further analogue Ph(2)PCH(2)CH(2)CH(2)SiHPr(n)()(2) (9) of A. A further analogue SiH(2)(CH(2)CH(2)CH(2)PPh(2))(2) (10) of biPSiH (B) is obtained similarly starting from SiH(2)(CH(2)CH=CH(2))(2). Steric control of silylalkyl cleavage from 2 is indicated by the fact that, like PPh(2)Cl (which forms B), two further biPSiH analogues SiH(Me)[CH(2)CH(2)CH(2)P(n-hex)(2)](2) (11) and SiH(Me)(CH(2)CH(2)CH(2)PPhBz)(2) (12) were obtained using P(n-hex)(2)Cl (i.e. n-hex = CH(3)(CH(2))(4)CH(2)-) or PPhBzCl (i.e. Bz = -CH(2)C(6)H(5)), respectively, whereas neither PPr(i)(2)Cl nor PBu(t)(2)Cl led to (phosphinoalkyl)silane formation

Memo of Readiness to Proceed with Phase 1 Privatization for the Tank Farm Contractor

International Nuclear Information System (INIS)

HONEYMAN, J.O.

2000-01-01

This Readiness to Proceed Memorandum provides the CH2M HILL Hanford Group, Inc. formal certification of readiness to proceed with provision of the waste feed and infrastructure to handle the products from the privatization contractor's waste processing plant. Summary information is included from the integrated scope-cost-schedule baseline, the analyses of the baseline, management systems, and systems reviews

Characterization of Vadose Zone Sediments Below the C Tank Farm: Borehole C4297 and RCRA Borehole 299-E27-22

Energy Technology Data Exchange (ETDEWEB)

Brown, Christopher F.; Serne, R. JEFFREY; Bjornstad, Bruce N.; Horton, Duane G.; Lanigan, David C.; Clayton, Ray E.; Valenta, Michelle M.; Vickerman, Tanya S.; Kutnyakov, Igor V.; Geiszler, Keith N.; Baum, Steven R.; Parker, Kent E.; Lindberg, Michael J.

2006-10-18

The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at Hanford. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) C. This report is the first of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from borehole C4297, installed adjacent to Tank C-105, and from borehole 299-E27-22, installed directly north of the C Tank Farm. Sediments from borehole 299-E27-22 were considered to be background uncontaminated sediments against which to compare contaminated sediments for the C Tank Farm characterization effort. This report also presents our interpretation of the data in the context of sediment types, the vertical extent of contamination, the migration potential of the contaminants, and the likely source of the contamination in the vadose zone and groundwater below the C Tank Farm. The information presented in this report supports the A-AX, C and U Waste Management Area field investigation report(a) in preparation by CH2M HILL Hanford Group, Inc. A core log was generated for both boreholes and a geologic evaluation of all core samples was performed at the time of opening. Aliquots of sediment from the borehole core samples were analyzed and characterized in the laboratory for the following parameters: moisture content, gamma-emitting radionuclides, one-to-one water extracts (which provide soil pH, electrical conductivity, cation, trace metal, and anion data), total carbon and inorganic carbon content, and 8 M nitric acid extracts (which provide a measure of the total leachable sediment content of contaminants). Two key radiocontaminants

Molecular Simulations and Theoretical Predictions for Adsorption and Diffusion of CH{sub 4}/H{sub 2} and CO{sub 2}/CH{sub 4} Mixtures in ZIFs

Energy Technology Data Exchange (ETDEWEB)

Liu, Jinchen; Keskin, Seda; Sholl, David S; Johnson, J. Karl

2011-05-01

Adsorption and diffusion of CO{sub 2}/CH{sub 4} and CH{sub 4}/H{sub 2} mixtures were computed in zeolite imidazolate frameworks (ZIFs), ZIF-68 and ZIF-70, using atomically detailed simulations. Adsorption selectivity, diffusion selectivity, and membrane selectivity of ZIFs were calculated based on the results of atomistic simulations. Mixture adsorption isotherms predicted by the ideal adsorbed solution theory agree well with the results of molecular simulations for both ZIFs. Mixture diffusivity calculations indicate that diffusion of CH{sub 4} is increased with increasing concentration of H{sub 2} in the CH{sub 4}/H{sub 2} mixture, while the diffusivity of H{sub 2} decreases with increasing CH{sub 4} concentration. In contrast, the diffusivity of CH{sub 4} is essentially independent of the concentration of CO{sub 2} in the CO{sub 2}/CH{sub 4} mixture, while CO{sub 2} diffusivity decreases with increased CH{sub 4} loading, even though the diffusivity of CH{sub 4} is substantially larger than that of CO{sub 2}. This unusual behavior can be explained in terms of differences in adsorption site preferences due to charge–quadrupole interactions.

The effects of CO addition on the autoignition of H-2, CH4 and CH4/H-2 fuels at high pressure in an RCM

NARCIS (Netherlands)

Gersen, Sander; Darmeveil, Harry; Levinsky, Howard

2012-01-01

Autoignition delay times of stoichiometric and fuel-lean (phi = 0.5) H-2, H-2/CO, CH4, CH4/CO, CH4/H-2 and CH4/CO/H-2 mixtures have been measured in an Rapid Compression Machine at pressures ranging from 20 to 80 bar and in the temperature range 900-1100K. The effects of CO addition on the ignition

P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

Science.gov (United States)

Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

2017-04-07

An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

Electrical Resistance of Ag-TS-S(CH2)(n-1)CH3//Ga2O3/EGaln Tunneling Junctions

NARCIS (Netherlands)

Cademartiri, Ludovico; Thuo, Martin M.; Nijhuis, Christian A.; Reus, William F.; Tricard, Simon; Barber, Jabulani R.; Sodhi, Rana N. S.; Brodersen, Peter; Kim, Choongik; Chiechi, Ryan C.; Whitesides, George M.

2012-01-01

Tunneling junctions having the structure Ag-TS-S(CH2)(n-1)CH3//Ga2O3/EGaIn allow physical-organic studies of charge transport across self-assembled monolayers (SAMs). In ambient conditions, the surface of the liquid metal electrode (EGaIn, 75.5 wt % Ga, 24.5 wt % In, mp 15.7 degrees C) oxidizes and

Temporal and spatial variations of soil CO2, CH4 and N2O fluxes at three differently managed grasslands

Directory of Open Access Journals (Sweden)

D. Imer

2013-09-01

Full Text Available A profound understanding of temporal and spatial variabilities of soil carbon dioxide (CO2, methane (CH4 and nitrous oxide (N2O fluxes between terrestrial ecosystems and the atmosphere is needed to reliably quantify these fluxes and to develop future mitigation strategies. For managed grassland ecosystems, temporal and spatial variabilities of these three soil greenhouse gas (GHG fluxes occur due to changes in environmental drivers as well as fertilizer applications, harvests and grazing. To assess how such changes affect soil GHG fluxes at Swiss grassland sites, we studied three sites along an altitudinal gradient that corresponds to a management gradient: from 400 m a.s.l. (intensively managed to 1000 m a.s.l. (moderately intensive managed to 2000 m a.s.l. (extensively managed. The alpine grassland was included to study both effects of extensive management on CH4 and N2O fluxes and the different climate regime occurring at this altitude. Temporal and spatial variabilities of soil GHG fluxes and environmental drivers on various timescales were determined along transects of 16 static soil chambers at each site. All three grasslands were N2O sources, with mean annual soil fluxes ranging from 0.15 to 1.28 nmol m−2 s−1. Contrastingly, all sites were weak CH4 sinks, with soil uptake rates ranging from −0.56 to −0.15 nmol m−2 s−1. Mean annual soil and plant respiration losses of CO2, measured with opaque chambers, ranged from 5.2 to 6.5 μmol m−2 s−1. While the environmental drivers and their respective explanatory power for soil N2O emissions differed considerably among the three grasslands (adjusted r2 ranging from 0.19 to 0.42, CH4 and CO2 soil fluxes were much better constrained (adjusted r2 ranging from 0.46 to 0.80 by soil water content and air temperature, respectively. Throughout the year, spatial heterogeneity was particularly high for soil N2O and CH4 fluxes. We found permanent hot spots for soil N2O emissions as well as

The use of CO 2 as an additive for ignition delay and pollutant control in CH 4 /air autoignition

KAUST Repository

Tingas, Efstathios Al.

2017-10-05

The effect of CO2 dilution on the adiabatic and isochoric autoignition of CH4/air mixtures is analyzed with Computational Singular Perturbation (CSP) algorithmic tools, with a particular emphasis on the determination of the features of the chemical dynamics that control ignition delay and emission formation. Increasing CO2 dilution causes longer ignition delays, lower final temperatures and decreased formation of NO and CO. These effects of CO2 dilution are shown to be entirely thermal, contrary to what happens with dilution with H2O, which also has chemical activity and can reduce ignition delay. For the same initial mole fraction of the diluent, the decrease in final temperature and in NO concentration is larger in the CO2 case whereas the decrease in CO is larger in the H2O case. The thermal effect of CO2 is entirely analogous with those of dilution with the chemically inert Ar, only stronger for the same percentage of initial dilution, because of the larger specific heat of CO2. The reactions that have the largest contribution to the characteristic explosive time scale of the system during ignition delay (H2O2(+M)→OH+OH(+M), CH3O2+CH2O→CH3O2H+HCO, CH4+CH3O2→CH3+CH3O2H, H+O2→O+OH, etc.) are not substantially affected by CO2 dilution, neither are the species that are pointed by CSP (CH3O2, H2O2, CH2O, etc.) as having the largest impact on the this timescale. The same holds for the modes that control CO and NO formation. The results point to the possibility of cold exhaust gas recirculation being used in order to produce mixtures with longer ignition delays and therefore substantial resistance to uncontrolled ignition.

Crystal structure and electrical conduction of the new organic-inorganic compound (CH2)2(NH3)2CdI4

Science.gov (United States)

Zhang, Liuqi; Wang, Jilin; Han, Feifei; Mo, Shuyi; Long, Fei; Gao, Yihua

2018-03-01

The new organic-inorganic compound (CH2)2(NH3)2CdI4 was prepared by slow evaporation method using a mixture solution of CdI2 and ethylenediamine iodide (EDAI) in the γ-butyrolactone (GBL). The synthesized compound was further characterized by single crystal diffraction, Infrared (IR) and Raman spectroscopy, energy dispersive spectrometer (EDS), X-Ray photoelectron spectroscopy (XPS) and thermogravimetric analysis. The relaxation behavior and conductivity mechanism of (CH2)2(NH3)2CdI4 was studied by the electrical impedance spectroscopy. The results indicated that (CH2)2(NH3)2CdI4 had a monoclinic structure with space group P21/c at room temperature. The complex impedance plotted as semicircle arcs and the proposed electrical equivalent circuit was to interpret the impedance behavior at different temperatures. The electrical equivalent circuit was made of a parallel combination of resistance (R) and fractal capacitance (CPE). Furthermore, the alternating current conductivity of the sample obeyed the Jonscher's law: σf =σdc + Afs and the conduction could be attributed to the correlated barrier hopping (CBH) model.

Air-sea fluxes of CO2 and CH4 from the Penlee Point Atmospheric Observatory on the south-west coast of the UK

Science.gov (United States)

Yang, Mingxi; Bell, Thomas G.; Hopkins, Frances E.; Kitidis, Vassilis; Cazenave, Pierre W.; Nightingale, Philip D.; Yelland, Margaret J.; Pascal, Robin W.; Prytherch, John; Brooks, Ian M.; Smyth, Timothy J.

2016-05-01

We present air-sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27 m above mean sea level, a.m.s.l.), each from a different period during 2014-2015. At sampling heights ≥ 18 m a.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable ( ≤ ±20 % in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air-sea exchange measurements in shelf regions. Covariance air-sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20 ± 3; 38 ± 3; 29 ± 6 µmole m-2 d-1 at 15, 18, 27 m a.m.s.l.) than during falling tides (14 ± 2; 22 ± 2; 21 ± 5 µmole m-2 d-1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air-sea CH4 flux by eddy covariance to be 20 µmole m-2 d-1 over hourly timescales (4 µmole m-2 d-1 over 24 h).

Characterization of Vadose Zone Sediments Below the TX Tank Farm: Boreholes C3830, C3831, C3832 and RCRA Borehole 299-W10-27

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Horton, Duane G.; Lanigan, David C.; Lindenmeier, Clark W.; Lindberg, Michael J.; Clayton, Ray E.; Legore, Virginia L.; Orr, Robert D.; Kutnyakov, Igor V.; Baum, Steven R.; Geiszler, Keith N.; Valenta, Michelle M.; Vickerman, Tanya S.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.8, 4.28,4.43, and 4.59. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in April 2004. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at Hanford. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) T-TX-TY. This report is the first of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from boreholes C3830, C3831, and C3832 in the TX Tank Farm, and from borehole 299-W-10-27 installed northeast of the TY Tank Farm.

Modified ZIF-8 mixed matrix membrane for CO2/CH4 separation

Science.gov (United States)

Nordin, Nik Abdul Hadi Md; Ismail, Ahmad Fauzi; Misdan, Nurasyikin; Nazri, Noor Aina Mohd

2017-10-01

Tunability of metal-organic frameworks (MOFs) properties enables them to be tailored for specific applications. In this study, zeolitic imidazole framework 8 (ZIF-8), sub-class of MOF, underwent pre-synthesis and post-synthesis modifications. The pre-synthesis modification using GO (ZIF-8/GO) shows slight decrease in textural properties, while the post-synthesis modification using amine solution (ZIF-8/NH2) resulted in superior BET surface area and pore volume. Mixed matrix membranes (MMMs) derived from polysulfone (PSf) and the modified ZIF-8s were then prepared via dry/wet phase inversion. The polymer chain flexibility of the resulted MMMs shows rigidification, where ZIF-8/NH2 as filler resulting higher rigidification compared to ZIF-8/GO. The MMMs were further subjected to pure CO2 and CH4 gas permeation experiments. The PSf/ZIF-8/NH2 shows superior CO2/CH4 selectivity (88% increased) while sacrificing CO2 permeance due to combination of severe polymer chain rigidification and the presence of CO2-philic group, amine. Whereas, the PSf/ZIF-8/GO possess 64% increase in CO2 permeance without notable changes in CO2/CH4 selectivity.

Antitumor activity of chLpMab-2, a human-mouse chimeric cancer-specific antihuman podoplanin antibody, via antibody-dependent cellular cytotoxicity.

Science.gov (United States)

Kaneko, Mika K; Yamada, Shinji; Nakamura, Takuro; Abe, Shinji; Nishioka, Yasuhiko; Kunita, Akiko; Fukayama, Masashi; Fujii, Yuki; Ogasawara, Satoshi; Kato, Yukinari

2017-04-01

Human podoplanin (hPDPN), a platelet aggregation-inducing transmembrane glycoprotein, is expressed in different types of tumors, and it binds to C-type lectin-like receptor 2 (CLEC-2). The overexpression of hPDPN is involved in invasion and metastasis. Anti-hPDPN monoclonal antibodies (mAbs) such as NZ-1 have shown antitumor and antimetastatic activities by binding to the platelet aggregation-stimulating (PLAG) domain of hPDPN. Recently, we developed a novel mouse anti-hPDPN mAb, LpMab-2, using the cancer-specific mAb (CasMab) technology. In this study we developed chLpMab-2, a human-mouse chimeric anti-hPDPN antibody, derived from LpMab-2. chLpMab-2 was produced using fucosyltransferase 8-knockout (KO) Chinese hamster ovary (CHO)-S cell lines. By flow cytometry, chLpMab-2 reacted with hPDPN-expressing cancer cell lines including glioblastomas, mesotheliomas, and lung cancers. However, it showed low reaction with normal cell lines such as lymphatic endothelial and renal epithelial cells. Moreover, chLpMab-2 exhibited high antibody-dependent cellular cytotoxicity (ADCC) against PDPN-expressing cells, despite its low complement-dependent cytotoxicity. Furthermore, treatment with chLpMab-2 abolished tumor growth in xenograft models of CHO/hPDPN, indicating that chLpMab-2 suppressed tumor development via ADCC. In conclusion, chLpMab-2 could be useful as a novel antibody-based therapy against hPDPN-expressing tumors. © 2017 The Authors. Cancer Medicine published by John Wiley & Sons Ltd.

Anomalous absorption in H2CN and CH2CN molecules

Indian Academy of Sciences (India)

Abstract. Structures of H2CN and CH2CN molecules are similar to that of H2CO mole- cule. The H2CO has shown anomalous absorption for its transition 111 − 110 at 4.8 GHz in a number of cool molecular clouds. Though the molecules H2CN and CH2CN have been identified in TMC-1 and Sgr B2 through some ...

Experimental and theoretical distribution of electron density and thermopolimerization in crystals of Ph3Sb(O2CCH=CH2)2 complex

Science.gov (United States)

Fukin, Georgy K.; Samsonov, Maxim A.; Arapova, Alla V.; Mazur, Anton S.; Artamonova, Tatiana O.; Khodorkovskiy, Mikhail A.; Vasilyev, Aleksander V.

2017-10-01

In this paper we present the results of a high-resolution single crystal X-ray diffraction experiment of a triphenylantimony diacrylate (Ph3Sb(O2CCH=CH2)2 (1)) and a subsequent charge density study based on a topological analysis according to quantum theory of atoms in molecules (QTAIM) together with density functional theory (DFT) calculation of isolated molecule. The QTAIM was used to investigate nature of the chemical bonds and molecular graph of Ph3Sb(O2CCH=CH2)2 complex. The molecular graph shows that only in one acrylate group there is an evidence of bonding between antimony and carbonyl oxygen atom in terms of the presence of a bond path. Thus the molecular graph for this class of compounds does not provide a definitive picture of the chemical bonding and should be complemented with other descriptors, such as and a source function (SF), noncovalent interaction (NCI) index and delocalization index (DI). Moreover the realization of π…π interactions between double bonds of acrylate groups in adjacent molecules allowed us to carry out a thermopolimerization reaction in crystals of Ph3Sb(O2CCH=CH2)2 complex and to determine a probable structure of polymer by solid state CP/MAS 13C NMR.

On the feasibility of chemi-ion formation in the system CH2CH(ã 4A″)+O(3P)

Science.gov (United States)

Metropoulos, Aristophanes

2003-12-01

We have investigated theoretically the possibility that the CH2CH(ã 4A″) radical can generate the CH2CHO+(X1A') ion upon collisions with O(3P). We have concluded that this is very unlikely because the minimum of the ground-state potential-energy surface of the ion is at about the same level as the potential energy of the asymptotic CH2CH(ã 4A″)+O(3P) fragments. In addition the Franck-Condon factors should not be favorable because of a drastic change in the geometry of the ion.

Budoucnost benzinových dvoutaktních motorů

OpenAIRE

Kříž, Jakub

2015-01-01

Práce se zabývá historickým vývojem dvoudobých benzínových motorů od samých počátků vzniku dvoudobého cyklu, mapuje technologický vývoj těchto motorů až do dnešní doby, kde je v druhé polovině pozornost věnována přímému srovnání motoru dvoudobého se čtyřdobým v oblasti ultralightových letounů. My thesis deals with the historical development of two-stroke petrol engines from the very establishment of a two-stroke cycle, mapping the technological development of these engines up to present da...

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Parks of Chapel Hill

Data.gov (United States)

Town of Chapel Hill, North Carolina — Hours, location, and amenity information for Chapel Hill parks as shown on the Town of Chapel Hill's website. Includes a map with points for each park location.

Betaine Phosphate (CH3)3N+CH2COO-.H3PO4 Modification Using D2O

International Nuclear Information System (INIS)

Saryati; Ridwan; Deswita; Sugiantoro, Sugik

2002-01-01

Betaine fosfate (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 modification by using D 2 O has been studied. This modification was carried out by slowly evaporation the saturated Betaine phosphat in the D 2 O solution in the dry box at 40 o C, until the dry crystal were formed. Based on the NMR data, can be concluded that the exchange process with D has been runed well and Betaine phosphate-D (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 has been resulted. From the X-ray diffraction pattern data can be concluded that there are a deference in the crystal structure between Betaine phosphate and Betaine phosphate modification result. From the Differential Scanning Colorimeter (DSC) diagram at the range temperature from 30 o C to 250 o C, can be shown that the Betaine phosphate-H has two endothermic transition phase, at 99 o C with a very little adsorbed calor and at 221.50 o C with -26.75 cal/g. Modified Betaine phosphate has also two endothermic transition phase, at 99.86 o C with -1.94 cal/g and at 171.01 o C with -3.48 cal/g. It can be conclosed that the D atom substitution on the H atoms in Betaine phosphate, to change the crystal and the endothermic fase temperature and energy

River Protection Project (RPP) Immobilized High-Level Waste (HLW) Interim Storage Plan

International Nuclear Information System (INIS)

BRIGGS, M.G.

2000-01-01

This document replaces HNF-1751, Revision 1. It incorporates updates to reflect changes in programmatic direction associated with the vitrification plant contract and associated DOE-ORP guidance. In addition it includes planning associated with failed/used melter and sample handling and disposition work scope. The document also includes format modifications and section numbering update consistent with CH2M HILL Hanford Group, Inc. procedures

Insertion and C-H Bond Activation of Unsaturated Substrates by Bis(benzamidinato)yttrium Alkyl, [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2), and Hydrido, {[PhC(NSiMe3)2]2Y(μ-H)}2, Compounds

NARCIS (Netherlands)

Duchateau, Robbert; Wee, Cornelis T. van; Teuben, Jan H.

1996-01-01

The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2) and {[PhC(NSiMe3)2]2Y(μ-H)}2 has been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation, or H/D exchange after hours at 100 °C in

Informační systém pro správu rezervací v restauracích

OpenAIRE

Slanař, David

2009-01-01

Tato bakalářská práce pojednává o stávajícím stavu fungování rezervací v restauracích a jeho inovaci pomocí zavedení informačního systému pro vytváření a správu rezervací. Popisuje návrh internetové webové aplikace umožňující on-line vytváření rezervací samotnými uživateli a jejich následnou správu zaměstnanci. Dále popis ekonomického přínosu a jiných výhod plynoucích ze zavedení tohoto systému v reálném světě a v neposlední řadě řešení případných problémů při nasazování systému v praxi. T...

Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

Science.gov (United States)

Grigorjeva, Liene; Daugulis, Olafs

2014-01-01

We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

Introducing ionic and/or hydrogen bonds into the SAM//Ga2O3 top-interface of Ag(TS)/S(CH2)nT//Ga2O3/EGaIn junctions.

Science.gov (United States)

Bowers, Carleen M; Liao, Kung-Ching; Yoon, Hyo Jae; Rappoport, Dmitrij; Baghbanzadeh, Mostafa; Simeone, Felice C; Whitesides, George M

2014-06-11

Junctions with the structure Ag(TS)/S(CH2)nT//Ga2O3/EGaIn (where S(CH2)nT is a self-assembled monolayer, SAM, of n-alkanethiolate bearing a terminal functional group T) make it possible to examine the response of rates of charge transport by tunneling to changes in the strength of the interaction between T and Ga2O3. Introducing a series of Lewis acidic/basic functional groups (T = -OH, -SH, -CO2H, -CONH2, and -PO3H) at the terminus of the SAM gave values for the tunneling current density, J(V) in A/cm(2), that were indistinguishable (i.e., differed by less than a factor of 3) from the values observed with n-alkanethiolates of equivalent length. The insensitivity of the rate of tunneling to changes in the terminal functional group implies that replacing weak van der Waals contact interactions with stronger hydrogen- or ionic bonds at the T//Ga2O3 interface does not change the shape (i.e., the height or width) of the tunneling barrier enough to affect rates of charge transport. A comparison of the injection current, J0, for T = -CO2H, and T = -CH2CH3--two groups having similar extended lengths (in Å, or in numbers of non-hydrogen atoms)--suggests that both groups make indistinguishable contributions to the height of the tunneling barrier.

Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

Science.gov (United States)

Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin

2015-01-01

The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

Insertion and C-H bond activation of unsaturated substrates by bis(benzamidinato)yttrium alkyl, [PhC(NSiMe(3))(2)](2)YR (R=CH(2)Ph center dot THF,CH(SiMe(3))(2)), and hydride, {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2), compounds

NARCIS (Netherlands)

Duchateau, R; vanWee, CT; Teuben, JH

1996-01-01

The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe(3))(2)](2)YR (R = CH(2)Ph . THF, CH(SiMe(3))(2) and {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2) have been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation or H/D exchange after

CH-TRU Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-10-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Geochemistry of PGE in mafic rocks of east Khasi Hills, Shillong ...

Indian Academy of Sciences (India)

study area. The studied mafic rocks of east Khasi Hills cover an area of about 4 km2 and represent .... In contrast to the global scenario, attempts for ..... chemical. Sp. no. structural mo de. Mineral comp o sition classification. M g#*. (wt%). (wt%).

Environmental controls of temporal and spatial variability in CO2 and CH4 fluxes in a neotropical peatland.

Science.gov (United States)

Wright, Emma L; Black, Colin R; Turner, Benjamin L; Sjögersten, Sofie

2013-12-01

Tropical peatlands play an important role in the global storage and cycling of carbon (C) but information on carbon dioxide (CO2) and methane (CH4) fluxes from these systems is sparse, particularly in the Neotropics. We quantified short and long-term temporal and small scale spatial variation in CO2 and CH4 fluxes from three contrasting vegetation communities in a domed ombrotrophic peatland in Panama. There was significant variation in CO2 fluxes among vegetation communities in the order Campnosperma panamensis > Raphia taedigera > Cyperus. There was no consistent variation among sites and no discernible seasonal pattern of CH4 flux despite the considerable range of values recorded (e.g. -1.0 to 12.6 mg m(-2) h(-1) in 2007). CO2 fluxes varied seasonally in 2007, being greatest in drier periods (300-400 mg m(-2) h(-1)) and lowest during the wet period (60-132 mg m(-2) h(-1)) while very high emissions were found during the 2009 wet period, suggesting that peak CO2 fluxes may occur following both low and high rainfall. In contrast, only weak relationships between CH4 flux and rainfall (positive at the C. panamensis site) and solar radiation (negative at the C. panamensis and Cyperus sites) was found. CO2 fluxes showed a diurnal pattern across sites and at the Cyperus sp. site CO2 and CH4 fluxes were positively correlated. The amount of dissolved carbon and nutrients were strong predictors of small scale within-site variability in gas release but the effect was site-specific. We conclude that (i) temporal variability in CO2 was greater than variation among vegetation communities; (ii) rainfall may be a good predictor of CO2 emissions from tropical peatlands but temporal variation in CH4 does not follow seasonal rainfall patterns; and (iii) diurnal variation in CO2 fluxes across different vegetation communities can be described by a Fourier model. © 2013 John Wiley & Sons Ltd.

Tc99m-pertechnetate thyroid scintigraphy in newborns with neonatal TSH levels > 20uUI/ml, detected in the national program of newborn screening of congenital hypothyroidism (CH)

International Nuclear Information System (INIS)

Lobo, G.; Ladron de Guevara, D.; Perez, A.; Donoso, G.; Jimenez, C.; Arnello, F.; Vivanco, X.

2002-01-01

The aim of this study was to analyse the thyroid scintigraphy (TS) findings in 279 newborn with neonatal TSH (TSHnn) levels above 20 uUI/ml, detected in the national program of newborn screening of CH and phenylketonuria, and to compare them with: 1) final diagnosis, estimating its positive (PPV) and negative predictive value (NPV) and 2) TSHnn levels. Materials and Method: Thyroid scintigraphy of 279 newborn (57.3% girls) who presented TSHnn levels > 20 uUI/ml were revised, classifying them in eutopic gland (EuG), ectopic gland (EcG) and absence of contrast (AC). EuG was classified by visual and quantitative criteria in: normal contrast and size, goiter, and decreased contrast (DC). Tc99m-pertechnetate TS was performed average at 19th life's day (SD:11 days) with a gammacamera- computer system. The patients were separated according to hormonal confirmatory levels in: CH, hyperthyrotropinaemia (HT) and euthyroid. We compared TS results with final diagnosis and also with TSHnn levels (>= or 50 uUI/ml group (p<0.001). Moreover, the former group presented bigger proportion of CH newborns and of EcG scans than < 50uUI/ml patients (p<0.001). EcG and goiter condition had a PPV for CH of 100% and 79.6%, respectively. The NPV of normal TS was 86.7%. Conclusion: 1) Newborns with TSHnn levels larger than 20 uUI/ml show a high frequency of abnormal TS. 2) The EcG is highly predictive of CH. 3) Goiter and AC associated to TSHnn levels above 50 uUI/ml support strongly CH diagnosis. 4) Normal TS correspond very likely to euthyroid newborn, specially when TSHnn is lower than 50 uUI/ml

Le temple-mémorial de Château-Thierry : approche monographique

Directory of Open Access Journals (Sweden)

Aline Magnien

2005-09-01

Full Text Available Le temple-mémorial de Château-Thierry, inauguré en 1924 est réalisé par deux architectes : Paul-Philippe Cret et Achille-Henri Chauquet, L’édifice est décoré d’un vitrail-tableau intitulé La Fayette nous voilà ! représentant La Fayette accueillant le général Pershing et de verrières ornées de scènes tirées des Paraboles de l’artiste suisse Eugène Burnand par son fils David Burnand. La chaire et le mobilier ont été offerts par des paroisses américaines en souvenir des soldats tombés au front. Par son architecture, son mobilier et les circonstances de la commande, le temple de Château-Thierry méritait une étude.The American memorial church of Château-Thierry, dedicated in 1924 has been built by two architects, Paul-Philippe Cret and Achille-Henri Chauquet. The church is adorned by a stained glass church window showing La Fayette welcoming Pershing and by some others stained glasses representing parables by David Burnand from sketches of his father Eugène Burnand. American churches supplied the pulpit and other furniture to adorn the building in memory of the soldiers died in the battle front. By its architecture, its furniture and the circumstances of its edification, the memorial church of Château-Thierry deserves a study

High-resolution sub-Doppler infrared spectroscopy of atmospherically relevant Criegee precursor CH2I radicals: CH2 stretch vibrations and "charge-sloshing" dynamics

Science.gov (United States)

Kortyna, A.; Lesko, D. M. B.; Nesbitt, D. J.

2018-05-01

The combination of a pulsed supersonic slit-discharge source and single-mode difference frequency direct absorption infrared spectroscopy permit first high resolution infrared study of the iodomethyl (CH2I) radical, with the CH2I radical species generated in a slit jet Ne/He discharge and cooled to 16 K in the supersonic expansion. Dual laser beam detection and collisional collimation in the slit expansion yield sub-Doppler linewidths (60 MHz), an absolute frequency calibration of 13 MHz, and absorbance sensitivities within a factor of two of the shot-noise limit. Fully rovibrationally resolved direct absorption spectra of the CH2 symmetric stretch mode (ν2) are obtained and fitted to a Watson asymmetric top Hamiltonian with electron spin-rotation coupling, providing precision rotational constants and spin-rotation tensor elements for the vibrationally excited state. Analysis of the asymmetric top rotational constants confirms a vibrationally averaged planar geometry in both the ground- and first-excited vibrational levels. Sub-Doppler resolution permits additional nuclear spin hyperfine structures to be observed, with splittings in excellent agreement with microwave measurements on the ground state. Spectroscopic data on CH2I facilitate systematic comparison with previous studies of halogen-substituted methyl radicals, with the periodic trends strongly correlated with the electronegativity of the halogen atom. Interestingly, we do not observe any asymmetric CH2 stretch transitions, despite S/N ≈ 25:1 on strongest lines in the corresponding symmetric CH2 stretch manifold. This dramatic reversal of the more typical 3:1 antisymmetric/symmetric CH2 stretch intensity ratio signals a vibrational transition moment poorly described by simple "bond-dipole" models. Instead, the data suggest that this anomalous intensity ratio arises from "charge sloshing" dynamics in the highly polar carbon-iodine bond, as supported by ab initio electron differential density plots and

Analysis of the laser photoelectron spectrum of CH-2

International Nuclear Information System (INIS)

Bunker, P.R.; Sears, T.J.

1985-01-01

We have simulated the photoelectron spectrum of CH - 2 using the model described previously [Sears and Bunker, J. Chem. Phys. 79, 5265 (1983)]. The optimization of the fit of the simulated spectrum to the recently observed spectrum of Lineberger and co-workers [J. Chem. Phys. 81, 1048 (1984) and preceding paper] has enabled us to determine the rotation-bending energy levels of triplet CH 2 over an energy range of more than 1 eV. It has also enabled us to determine that the rotational temperature of the CH - 2 in the experiment is 220 K and that, for v 2 = 1, the vibrational temperature is 680 K. For CH - 2 we determine that a/sub e/ = 103 0 and that ν 2 = 1230 cm -1 . The singlet--triplet splitting in methylene is determined to be 3150 +- 30 cm -1 (0.3905 +- 0.004 eV, 9.01 +- 0.09 kcal/mol) from the photoelectron spectrum, in excellent agreement with the more accurate value previously obtained from LMR spectroscopy [McKellar et al., J. Chem. Phys. 79, 5251 (1983)] of 3165 +- 20 cm -1 (0.3924 +- 0.0025 eV, 9.05 +- 0.06 kcal/mol), and the electron affinity of triplet CH 2 is determined to be 0.652 +- 0.006 eV

Cavity ring down spectroscopy of CH, CH2, HCO, and H2CO in a premixed flat flame at both atmospheric and sub-atmospheric pressure

NARCIS (Netherlands)

Evertsen, R.; Staicu, A.D.; Oijen, van J.A.; Dam, N.J.; Goey, de L.P.H.; Meulen, ter J.J.; Cheauveau, C.; Vovelle, C.

2003-01-01

Density distributions of CH, CH2, HCO and H2CO have been measured in a premixed CH4/air flat flame by Cavity Ring Down Spectroscopy (CRDS). At atmospheric pressure problems are encountered due to the narrow spatial distribution of these species. Rotational flame Temperatures have been derived from

Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

Science.gov (United States)

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

1997-01-01

Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

Carbon dynamics and CO2 and CH4 outgassing in the Mekong delta

Science.gov (United States)

Borges, Alberto V.; Abril, Gwenaël; Bouillon, Steven

2018-02-01

We report a data set of biogeochemical variables related to carbon cycling obtained in the three branches (Mỹ Tho, Hàm Luông, Cố Chiên) of the Mekong delta (Bến Tre province, Vietnam) in December 2003, April 2004, and October 2004. Both the inner estuary (upstream of the mouth) and the outer estuary (river plume) were sampled, as well as side channels. The values of the partial pressure of CO2 (pCO2) ranged between 232 and 4085 ppm, O2 saturation level (%O2) between 63 and 114 %, and CH4 between 2 and 2217 nmol L-1, within the ranges of values previously reported in temperate and tropical meso- and macro-tidal estuaries. Strong seasonal variations were observed. In the upper oligohaline estuary, low pCO2 (479-753 ppm) and high %O2 (98-106 %) values were observed in April 2004 most probably related to freshwater phytoplankton growth owing to low freshwater discharge (1400 m3 s-1) and increase in water residence time; during the two other sampling periods with a higher freshwater discharge (9300-17 900 m3 s-1), higher pCO2 (1895-2664 ppm) and lower %O2 (69-84 %) values were observed in the oligohaline part of the estuary. In October 2004, important phytoplankton growth occurred in the offshore part of the river plume as attested by changes in the contribution of particulate organic carbon (POC) to total suspended matter (TSM) (%POC) and the stable isotope composition of POC (δ13C-POC), possibly related to low TSM values (improvement of light conditions for phytoplankton development), leading to low pCO2 (232 ppm) and high %O2 (114 %) values. Water in the side channels in the Mekong delta was strongly impacted by inputs from the extensive shrimp farming ponds. The values of pCO2, CH4, %O2, and the stable isotope composition of dissolved inorganic carbon (δ13C-DIC) indicated intense organic matter degradation that was partly mediated by sulfate reduction in sediments, as revealed by the slope of total alkalinity (TA) and DIC covariations. The δ13C

Detection of transient infrared absorption of SO3 and 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] in the reaction CH2OO+SO2

Science.gov (United States)

Wang, Yi-Ying; Dash, Manas Ranjan; Chung, Chao-Yu; Lee, Yuan-Pern

2018-02-01

We recorded time-resolved infrared absorption spectra of transient species produced on irradiation at 308 nm of a flowing mixture of CH2I2/O2/N2/SO2 at 298 K. Bands of CH2OO were observed initially upon irradiation; their decrease in intensity was accompanied by the appearance of an intense band at 1391.5 cm-1 that is associated with the degenerate SO-stretching mode of SO3, two major bands of HCHO at 1502 and 1745 cm-1, and five new bands near >1340, 1225, 1100, 940, and 880 cm-1. The band near 1340 cm-1 was interfered by absorption of SO2 and SO3, so its band maximum might be greater than 1340 cm-1. SO3 in its internally excited states was produced initially and became thermalized at a later period. The rotational contour of the band of thermalized SO3 agrees satisfactorily with the reported spectrum of SO3. These five new bands are tentatively assigned to an intermediate 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] according to comparison with anharmonic vibrational wavenumbers and relative IR intensities predicted for this intermediate. Observation of a small amount of cyc-(CH2)O(SO2)O is consistent with the expected reaction according to the potential energy scheme predicted previously. SO3+HCHO are the major products of the title reaction. The other predicted product channel HCOOH+SO2 was unobserved and its branching ratio was estimated to be <5%.

Reaction of ether and thioether functionalised 1-alkenes with the cationic permethylzirconocene olefin polymerisation catalyst [(eta(5)-C5Me5)(2)ZrMe](+). Molecular structure of the insertion product [(eta(5)-C5Me5)(2)ZrCH2CH(Me)CH2OEt](+)

NARCIS (Netherlands)

Bijpost, Erik A; Zuideveld, Martin A.; Meetsma, Auke; Teuben, Jan H

1998-01-01

Reaction of [(η5-C5Me5)2ZrMe][MeB(C6F5)3] (1) with (thio)ether functionalised alkenes: 3-ethoxy-1-propene and 3-(methylthio)-1-propene gives stable insertion products [(η5-C5Me5)2ZrCH2CH(Me)CH2XR][MeB(C6F5)3] (2: X = O, R = Et; 3: X = S, R = Me) in which the (thio)ether function is intramolecularly

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Seasonal changes of CO2, CH4 and N2O fluxes in relation to land-use change in tropical peatlands located in coastal area of South Kalimantan

International Nuclear Information System (INIS)

Inubushi, K.; Furukawa, Y.; Hadi, A.; Purnomo, E.; Tsuruta, H.

2003-01-01

Tropical peatland could be a source of greenhouse gases emission because it contains large amounts of soil carbon and nitrogen. However these emissions are strongly influenced by soil moisture conditions. Tropical climate is characterized typically by wet and dry seasons. Seasonal changes in the emission of carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O) were investigated over a year at three sites (secondary forest, paddy field and upland field) in the tropical peatland in South Kalimantan, Indonesia. The amount of these gases emitted from the fields varied widely according to the seasonal pattern of precipitation, especially methane emission rates were positively correlated with precipitation. Converting from secondary forest peatland to paddy field tended to increase annual emissions of CO 2 and CH 4 to the atmosphere (from 1.2 to 1.5 kg CO 2 -C m -2 y -1 and from 1.2 to 1.9 g CH 4 -C m -2 y -1 ), while changing land-use from secondary forest to upland tended to decrease these gases emissions (from 1.2 to 1.0 kg CO 2 -C m -2 y -1 and from 1.2 to 0.6 g CH 4 -C m -2 y -1 ), but no clear trend was observed for N 2 O which kept negative value as annual rates at three sites. (Author)

Needs Analysis for Dimethyl Mercury

Energy Technology Data Exchange (ETDEWEB)

Schmoldt, Michael J.

2013-02-13

For this needs analysis, a total of 131 DMHg analytical results were collected and reviewed from the Hanford Tank Farms from 2004 to 2007. Sampling data from the Site Wide Industrial Hygiene Database (SWIHO), the Tank waste inventory System (TWINs), and prior sampling campaigns by CH2M Hill Hanford that were not available in the SWIHD database, were aggregated for analysis. Technical literature used by the Savannah River Site (SRS). Bechtel RPP·WTP, and CH2M Hill Hanford from 2003-2007, were also reviewed to identify potential DMHg exposure concerns applicable to the tank farms. After analyzing the adequacy of lhe data, information gaps were identified and recommendations for corrective actions items were developed.

Needs Analysis for Dimethyl Mercury

International Nuclear Information System (INIS)

Schmoldt, Michael J.

2013-01-01

For this needs analysis, a total of 131 DMHg analytical results were collected and reviewed from the Hanford Tank Farms from 2004 to 2007. Sampling data from the Site Wide Industrial Hygiene Database (SWIHO), the Tank waste inventory System (TWINs), and prior sampling campaigns by CH2M Hill Hanford that were not available in the SWIHD database, were aggregated for analysis. Technical literature used by the Savannah River Site (SRS). Bechtel RPPAWTP, and CH2M Hill Hanford from 2003-2007, were also reviewed to identify potential DMHg exposure concerns applicable to the tank farms. After analyzing the adequacy of lhe data, information gaps were identified and recommendations for corrective actions items were developed

Optimizing hill seeding density for high-yielding hybrid rice in a single rice cropping system in South China.

Directory of Open Access Journals (Sweden)

Danying Wang

Full Text Available Mechanical hill direct seeding of hybrid rice could be the way to solve the problems of high seeding rates and uneven plant establishment now faced in direct seeded rice; however, it is not clear what the optimum hill seeding density should be for high-yielding hybrid rice in the single-season rice production system. Experiments were conducted in 2010 and 2011 to determine the effects of hill seeding density (25 cm×15 cm, 25 cm×17 cm, 25 cm×19 cm, 25 cm×21 cm, and 25 cm×23 cm; three to five seeds per hill on plant growth and grain yield of a hybrid variety, Nei2you6, in two fields with different fertility (soil fertility 1 and 2. In addition, in 2012 and 2013, comparisons among mechanical hill seeding, broadcasting, and transplanting were conducted with three hybrid varieties to evaluate the optimum seeding density. With increases in seeding spacing from 25 cm×15 cm to 25 cm×23 cm, productive tillers per hill increased by 34.2% and 50.0% in soil fertility 1 and 2. Panicles per m2 declined with increases in seeding spacing in soil fertility 1. In soil fertility 2, no difference in panicles per m2 was found at spacing ranging from 25 cm×17 cm to 25 cm×23 cm, while decreases in the area of the top three leaves and aboveground dry weight per shoot at flowering were observed. Grain yield was the maximum at 25 cm×17 cm spacing in both soil fertility fields. Our results suggest that a seeding density of 25 cm×17 cm was suitable for high-yielding hybrid rice. These results were verified through on-farm demonstration experiments, in which mechanical hill-seeded rice at this density had equal or higher grain yield than transplanted rice.

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2007-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2006-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2004-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2008-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-09-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-05-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-02-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codesand corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-12-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-01-18

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-10-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-03-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-09-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-12-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-11-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-12-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-30

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-06-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Simulations and experimental investigations of the competitive adsorption of CH4 and CO2 on low-rank coal vitrinite.

Science.gov (United States)

Yu, Song; Bo, Jiang; Jiahong, Li

2017-09-16

The mechanism for the competitive adsorption of CH 4 and CO 2 on coal vitrinite (DV-8, maximum vitrinite reflectance R o,max  = 0.58%) was revealed through simulation and experimental methods. A saturated state was reached after absorbing 17 CH 4 or 22 CO 2 molecules per DV-8 molecule. The functional groups (FGs) on the surface of the vitrinite can be ranked in order of decreasing CH 4 and CO 2 adsorption ability as follows: [-CH 3 ] > [-C=O] > [-C-O-C-] > [-COOH] and [-C-O-C-] > [-C=O] > [-CH 3 ] > [-COOH]. CH 4 and CO 2 distributed as aggregations and they were both adsorbed at the same sites on vitrinite, indicating that CO 2 can replace CH 4 by occupying the main adsorption sites for CH 4 -vitrinite. High temperatures are not conducive to the adsorption of CH 4 and CO 2 on vitrinite. According to the results of density functional theory (DFT) and grand canonical Monte Carlo (GCMC) calculations, vitrinite has a higher adsorption capacity for CO 2 than for CH 4 , regardless of whether a single-component or binary adsorbate is considered. The equivalent adsorption heat (EAH) of CO 2 -vitrinite (23.02-23.17) is higher than that of CH 4 -vitrinite (9.04-9.40 kJ/mol). The EAH of CO 2 -vitrinite decreases more rapidly with increasing temperature than the EAH of CH 4 -vitrinite does, indicating in turn that the CO 2 -vitrinite bond weakens more quickly with increasing temperature than the CH 4 -vitrinite bond does. Simulation data were found to be in good accord with the corresponding experimental results.

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH)

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, M. D.

2005-01-01

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy...

Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical—an intermediate formed in the OH + allene reaction en route to CH3 + ketene

Science.gov (United States)

Alligood, Bridget W.; FitzPatrick, Benjamin L.; Szpunar, David E.; Butler, Laurie J.

2011-02-01

We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH3C(O)CH2 radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH3CO and CH2Cl. The CH3C(O)CH2 radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH3 + ketene. The 193 nm photodissociation laser allows us to produce these CH3C(O)CH2 radicals with enough internal energy to span the dissociation barrier leading to the CH3 + ketene asymptote. Therefore, some of the vibrationally excited CH3C(O)CH2 radicals undergo subsequent dissociation to CH3 + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH3 and COCH2Cl fragments. The CH3C(O)CH2 radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S1 surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH3 + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.

Assessment of CH4 and N2O fluxes in a Danish Beech (Fagus sylvatica) forest and an adjacent N-fertilised barley (Hordeum vulgare)

DEFF Research Database (Denmark)

Ambus, P.; Jensen, J.M.; Prieme, A.

2001-01-01

Fluxes of CH4 and N2O were measured regularly in an agricultural field treated with 280 g m(-2) of sewage sludge. In a nearby beech forest N2O and CH4 fluxes were measured in a well-drained (dry) area and in a wet area adjacent to a drainage canal. We observed brief increases of both CH4 and N2O...... and independent of drainage status. Methane oxidation was observed all-year round in the forest cumulating to -225 mg C m(-2) and -84 mg C m(-2) in dry and wet areas. In a model experiment with incubated soil cores, nitrogen amendment (NH4Cl) and perturbation significantly reduced CH4 oxidation in the forest soil...... sludge, respectively. Four months after the sludge applications a significant effect on CO2 and NO emissions was still obvious in the field, the latter perhaps due to elevated nitrification. Nitrous oxide emission in the beech forest was about six times smaller (45 mg N m(-2)) than in the field...

Rozhraní typu I2C a jejich implementační možnosti v technologiích ASIC

OpenAIRE

Podzemný, Jakub

2016-01-01

Práce se zabývá možnostmi implementace I2C, SMBus a PMBus rozhraní v současných technologiích ASIC. V první části se práce zaměřuje na popis jednotlivých sběrnic a jejich vzájemných rozdílů dle nejnovějších specifikací z digitálního a funkčního pohledu. Analogová část problematiky je zde z velké části zanedbána. Dále se práce zabývá porovnáním vybraných I2C/SMBus slave modulů vytvořených firmou ON Semiconductor, popsaných v jazyce Verilog HDL, z hlediska počtu klopných obvodů, funkčnosti a př...

Complex methyl groups dynamics in [(CH3)4P]3Sb2Br9 (PBA) from low to high temperatures by proton spin-lattice relaxation and narrowing of proton NMR spectrum.

Science.gov (United States)

Latanowicz, L; Medycki, W; Jakubas, R

2009-11-01

Molecular dynamics of a polycrystalline sample of [(CH(3))(4)P](3)Sb(2)Br(9) (PBA) has been studied on the basis of the T(1) (24.7 MHz) relaxation time measurement, the proton second moment of NMR and the earlier published T(1) (90 MHz) relaxation times. The study was performed in a wide range of temperatures (30-337 K). The tunnel splitting omega(T) of the methyl groups was estimated as of low frequency (from kHz to few MHz). The proton spin pairs of the methyl group are known to perform a complex internal motion being a resultant of four components. Three of them involve mass transportation over and through the potential barrier and are characterized by the correlation times tau(3) and tau(T)of the jumps over the barrier and tunnel jumps in the threefold potential of the methyl group and tau(iso) the correlation time of isotropic rotation of the whole TMP cation. For tau(3) and tau(iso) the Arrhenius temperature dependence was assumed, while for tau(T)--the Schrödinger one. The fourth motion causes fluctuations of the tunnel splitting frequency, omega(T), and it is related to the lifetime of the methyl spin at the energy level. The correlation function for this fourth motion (tau(omega) correlation time) has been proposed by Müller-Warmuth et al. In this paper a formula for the correlation function and spectral density of the complex motion made of the above-mentioned four components was derived and used in interpretation of the T(1) relaxation time. The second moment of proton NMR line at temperatures below 50K is four times lower than its value for the rigid structure. The three components of the internal motion characterized by tau(T), tau(H), and tau(iso) were proved to reduce the second moment of the NMR line. The tunnel jumps of the methyl group reduce M(2) at almost 0K, the classical jumps over the barrier reduce M(2) in the vicinity of 50K, while the isotropic motion near 150K. Results of the study on the dynamics of CH(3) groups of TMP cation based on

Comprehensive effects of a sedge plant on CH4 and N2O emissions in an estuarine marsh

Science.gov (United States)

Li, Yangjie; Wang, Dongqi; Chen, Zhenlou; Hu, Hong

2018-05-01

Although there have been numerous studies focusing on plants' roles in methane (CH4) emissions, the influencing mechanism of wetland plants on nitrous oxide (N2O) emissions has rarely been studied. Here, we test whether wetland plants also play an important role in N2O emissions. Gas fluxes were determined using the in situ static flux chamber technique. We also carried out pore-water extractions, sedge removal experiments and tests of N2O transportation. The brackish marsh acted as a net source of both CH4 and N2O. However, sedge plants played the opposite role in CH4 and N2O emissions. The removal of the sedges led to reduced CH4 emissions and increased accumulation of CH4 inside the sediment. Apart from being a conduit for CH4 transport, the sedges made a greater contribution to CH4 oxidation than CH4 production. The sedges exerted inhibitory effects on the release of N2O. The N2O was barely detectable inside the sediment in both vegetated and vegetation-removed plots. The denitrification measurements and nitrogen addition (the addition rates were equal to 0.028, 0.056 and 0.112 g m-2) experiments suggest that denitrification associated with N2O production occurred mainly in the surface sediment layer. The vascular sedge could transport atmospheric N2O downward into the rhizosphere. The rhizospheric sediment, together with the vascular sedge, became an effective sink of atmospheric N2O.

Densities, viscosities, and refractive indexes for {C2H5CO2(CH2)2CH3+C6H13OH+C6H6} at T=308.15 K

International Nuclear Information System (INIS)

Casas, Herminio; Garcia-Garabal, Sandra; Segade, Luisa; Cabeza, Oscar.; Franjo, Carlos; Jimenez, Eulogio

2003-01-01

In this work we present densities, kinematic viscosities, and refractive indexes of the ternary system {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH+C 6 H 6 } and the corresponding binary mixtures {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 6 }, {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH}, and {C 6 H 13 OH+C 6 H 6 }. All data have been measured at T=308.15 K and atmospheric pressure over the whole composition range. The excess molar volumes, dynamic viscosity deviations, and changes of the refractive index on mixing were calculated from experimental measurements. The results for binary mixtures were fitted to a polynomial relationship to estimate the coefficients and standard deviations. The Cibulka equation has been used to correlate the experimental values of ternary mixtures. Also, the experimental values obtained for the ternary mixture were used to test the empirical methods of Kohler, Jacob and Fitzner, Colinet, Tsao and Smith, Toop, Scatchard et al., and Hillert. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, McAllister, Auslaender, and Teja-Rice. Finally, the experimental refractive indexes were compared with the predicted results for the Lorentz-Lorenz, Gladstone-Dale, Wiener, Heller, and Arago-Biot equations. In all cases, we give the standard deviation between the experimental data and that calculated with the above named relations

River Protection Project (RPP) Immobilized Low- Ativity Waste (ILAW) Disposal Plan

International Nuclear Information System (INIS)

BRIGGS, M.G.

2000-01-01

This document replaces HNF-1517, Rev 2 which is deleted. It incorporates updates to reflect changes in programmatic direction associated with the vitrification plant contract change and associated DOE/ORP guidance. In addition it incorporates the cancellation of Project W-465, Grout Facility, and the associated modifications to Project W-520, Immobilized High-Level Waste Disposal Facility. It also includes document format changes and section number modifications consistent with CH2M HILL Hanford Group, Inc. procedures

Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

Science.gov (United States)

Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

2013-01-01

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Characterization of Vadose Zone Sediments Below the T Tank Farm: Boreholes C4104, C4105, 299-W10-196, and RCRA Borehole 299-W11-39

Energy Technology Data Exchange (ETDEWEB)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Horton, Duane G.; Lanigan, David C.; Schaef, Herbert T.; Lindenmeier, Clark W.; Lindberg, Michael J.; Clayton, Ray E.; Legore, Virginia L.; Geiszler, Keith N.; Baum, Steven R.; Valenta, Michelle M.; Kutnyakov, Igor V.; Vickerman, Tanya S.; Orr, Robert D.; Brown, Christopher F.

2008-09-11

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.8, 4.28, and 4.52. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in September 2004. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at Hanford. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) T-TX-TY. This report is the second of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from boreholes C4104 and C4105 in the T Tank Farm, and from borehole 299-W-11-39 installed northeast of the T Tank Farm. Finally, the measurements on sediments from borehole C4104 are compared with a nearby borehole drilled in 1993, 299- W10-196, through the tank T-106 leak plume.

Kinetics of the R + HBr {r_reversible} RH + Br (CH{sub 3}CHBr, CHBr{sub 2} or CDBr{sub 2}) equilibrium. Thermochemistry of the CH{sub 3}CHBr and CHBr{sub 2} radicals

Energy Technology Data Exchange (ETDEWEB)

Seetula, Jorma A. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014 University of Helsinki, Helsinki (Finland)], E-mail: j.seetula@kolumbus.fi; Eskola, Arkke J. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014 University of Helsinki, Helsinki (Finland)

2008-07-03

The kinetics of the reaction of the CH{sub 3}CHBr, CHBr{sub 2} or CDBr{sub 2} radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH{sub 3}CHBr (or CHBr{sub 2} or CDBr{sub 2}) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH{sub 3}CHBr{sub 2} (or CHBr{sub 3} or CDBr{sub 3}). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH{sub 3}CHBr + HBr) and from 288 to 477 K (CHBr{sub 2} + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1{sigma} + Student's t values, units in cm{sup 3} molecule{sup -1} s{sup -1}, no error limits for the third reaction): k(CH{sub 3}CHBr + HBr) = (1.7 {+-} 1.2) x 10{sup -13} exp[+ (5.1 {+-} 1.9) kJ mol{sup -1}/RT], k(CHBr{sub 2} + HBr) = (2.5 {+-} 1.2) x 10{sup -13} exp[-(4.04 {+-} 1.14) kJ mol{sup -1}/RT] and k(CDBr{sub 2} + HBr) = 1.6 x 10{sup -13} exp(-2.1 kJ mol{sup -1}/RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH{sub 3}CHBr and CHBr{sub 2} radicals and an experimental entropy value at 298 K for the CH{sub 3}CHBr radical were obtained using a second-law method. The result for the entropy value for the CH{sub 3}CHBr radical is 305 {+-} 9 J K{sup -1} mol{sup -1}. The results for the enthalpy of formation values at 298 K are (in kJ mol{sup -1}): 133.4 {+-} 3.4 (CH{sub 3}CHBr) and 199.1 {+-} 2.7 (CHBr{sub 2}), and for {alpha}-C-H bond dissociation energies of analogous compounds are (in kJ mol{sup -1}): 415.0 {+-} 2.7 (CH{sub 3}CH{sub 2}Br) and 412.6 {+-} 2.7 (CH{sub 2}Br{sub 2}), respectively.

Postoje univerzitních studentů pedagogicky orientovaných studijních programů k homosexualitě měřené na škále Homosexuality Attitude Scale/ Attitudes of university students of educationally-oriented study programs towards homosexuality measured on the Homosexuality Attitude Scale

Directory of Open Access Journals (Sweden)

Petr Hlaďo

2015-03-01

Full Text Available Cílem studie je zhodnotit postoje studentů pedagogicky orientovaných studijních programů k homosexualitě a zjistit, čím jsou ovlivněny. V příspěvku je argumentován význam tématu v rámci pedagogiky, podán přehled závěrů vybraných českých a zahraničních výzkumů vztahujících se k problematice postojů heterosexuálů k homosexualitě. Dále jsou prezentovány cíle, metodologie a poznatky z vlastního výzkumného šetření. V závěru jsou prezentována doporučení pro pregraduální vzdělávání budoucích pedagogů a podány návrhy pro další výzkum. Cílem výzkumu bylo zjistit postoje studentů pedagogicky orientovaných studijních programů k homosexualitě. Použitým výzkumným nástrojem byl dotazník Kiteové a Deauxové – Homosexuality Attitude Scale (Cronbachovo alfa = 0,91. Sběr dat proběhl v říjnu a listopadu 2014. Výběrový soubor je tvořen 1 140 respondenty. Studenti pedagogických studijních programů mají v průměrném hodnocení k homosexualitě poměrně pozitivní postoje (průměrné skóre HAS = 88,77 z teoretického rozmezí 12–105, nižší hodnota indikuje negativnější postoj k homosexualitě. Signifikantně negativnější postoje k homosexualitě byly zjištěny u mužů, studentů nižších ročníků studia a příslušníků římsko-katolické či jiné církve nebo náboženské společnosti. Z poznatků vyplývá potřeba formování postojů budoucích pedagogů k homosexualitě kombinací kognitivně-afektivních intervencí v rámci formálního vzdělávání.

A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma.

Science.gov (United States)

Ovanesyan, Rafaiel A; Hausmann, Dennis M; Agarwal, Sumit

2018-06-06

We report a novel three-step SiN x atomic layer deposition (ALD) process using Si 2 Cl 6 , CH 3 NH 2 , and N 2 plasma. In a two-step process, nonhydrogenated chlorosilanes such as Si 2 Cl 6 with N 2 plasmas lead to poor-quality SiN x films that oxidize rapidly. The intermediate CH 3 NH 2 step was therefore introduced in the ALD cycle to replace the NH 3 plasma step with a N 2 plasma, while using Si 2 Cl 6 as the Si precursor. This three-step process lowers the atomic H content and improves the film conformality on high-aspect-ratio nanostructures as Si-N-Si bonds are formed during a thermal CH 3 NH 2 step in addition to the N 2 plasma step. During ALD, the reactive surface sites were monitored using in situ surface infrared spectroscopy. Our infrared spectra show that, on the post-N 2 plasma-treated SiN x surface, Si 2 Cl 6 reacts primarily with the surface -NH 2 species to form surface -SiCl x ( x = 1, 2, or 3) bonds, which are the reactive sites during the CH 3 NH 2 cycle. In the N 2 plasma step, reactive -NH 2 surface species are created because of the surface H available from the -CH 3 groups. At 400 °C, the SiN x films have a growth per cycle of ∼0.9 Å with ∼12 atomic percent H. The films grown on high-aspect-ratio nanostructures have a conformality of ∼90%.

Radiative association of CH3(+) and H2

International Nuclear Information System (INIS)

Bates, D.R.

1985-01-01

The temperature variation of the rate coefficient for k(1) for CH3(+) + H2 yields CH5(+) + hv is computed treating the para and ortho forms of H2 separately, taking account of nuclear spin and using an accurate theory of the kinetics of association. The results are made absolute with the aid of the measurement at 13 K by Barlow et al. (1984). By combining this measurement with the CH5(+) vibrational frequencies obtained by Pople (1984) from a quantal study, it is deduced that the probability of the stabilizing radiative transition is 5400/s. The rate coefficients k(1) (T, para) and k(1) (T, ortho) are given at 13 K, 30 K, and 80 K. 23 references

Rozvoj obchodních aktivit firmy prostřednictvím franchisingu

OpenAIRE

Pavlík, Jakub

2012-01-01

Diplomová práce pojednává o rozvoji obchodních aktivit vybraného subjektu prostřednictvím franchisingového podnikání. Předmětem práce je definování teoretických východisek z oblasti franchisingu, provedení analýzy současného stavu společnosti AQUAdesign s.r.o. a vytvoření návrhu franchisingového konceptu dané společnosti. Návrhová část práce je poté doplněna o příslušný harmonogram implementace. The master´s thesis deals the development of the business activity selected subject through fra...

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and α-lactone recorded in gaseous reactions of CH3CO and O2

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-01

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH3CO and O2; IR absorption spectra of CH3C(O)OO and α-lactone were observed. Absorption bands with origins at 1851±1, 1372±2, 1169±6, and 1102±3 cm-1 are attributed to t-CH3C(O)OO, and those at 1862±3, 1142±4, and 1078±6 cm-1 are assigned to c-CH3C(O)OO. A weak band near 1960 cm-1 is assigned to α-lactone, cyc-CH2C(O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH3C(O)OO is more stable than c-CH3C(O)OO by 3±2 kJ mol-1. Based on these observations, the branching ratio for the OH+α-lactone channel of the CH3CO+O2 reaction is estimated to be 0.04±0.01 under 100 Torr of O2 at 298 K. A simple kinetic model is employed to account for the decay of CH3C(O)OO.

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and alpha-lactone recorded in gaseous reactions of CH3CO and O2.

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-21

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH(3)CO and O(2); IR absorption spectra of CH(3)C(O)OO and alpha-lactone were observed. Absorption bands with origins at 1851+/-1, 1372+/-2, 1169+/-6, and 1102+/-3 cm(-1) are attributed to t-CH(3)C(O)OO, and those at 1862+/-3, 1142+/-4, and 1078+/-6 cm(-1) are assigned to c-CH(3)C(O)OO. A weak band near 1960 cm(-1) is assigned to alpha-lactone, cyc-CH(2)C(=O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH(3)C(O)OO is more stable than c-CH(3)C(O)OO by 3+/-2 kJ mol(-1). Based on these observations, the branching ratio for the OH+alpha-lactone channel of the CH(3)CO+O(2) reaction is estimated to be 0.04+/-0.01 under 100 Torr of O(2) at 298 K. A simple kinetic model is employed to account for the decay of CH(3)C(O)OO.

Selective photocatalytic reduction of CO{sub 2} by H{sub 2}O/H{sub 2} to CH{sub 4} and CH{sub 3}OH over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalyst

Energy Technology Data Exchange (ETDEWEB)

Tahir, Muhammad, E-mail: mtahir@cheme.utm.my [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Punjab (Pakistan); Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia)

2016-12-15

Highlights: • Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalysts tested for CO{sub 2} photoreduction with H{sub 2}O/H{sub 2}. • Production of CH{sub 4} and CH{sub 3}OH depends on reductants type and metal-loading to TiO{sub 2}. • CH{sub 4} production over Cu-In/TiO{sub 2} was 1.5 fold more than In/TiO{sub 2} and 5 times the TiO{sub 2}. • The Cu-promoted CH{sub 3}OH production while In gave more CH{sub 4} with water vapors. • The H{sub 2} reductant gave negative effect for CH{sub 4} but enhanced CH{sub 3}OH production. - Abstract: Photocatalytic CO{sub 2} reduction by H{sub 2}O and/or H{sub 2} reductant to selective fuels over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N{sub 2} adsorption-desorption, UV–vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO{sub 2}, oxidized as Cu{sup 2+} and In{sup 3+}, promoted efficient separation of photo-generated electron/hole pairs (e{sup −}/h{sup +}). The results indicate that the reduction rate of CO{sub 2} by H{sub 2}O to CH{sub 4} approached to 181 μmol g{sup −1} h{sup −1} using 0.5% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst, a 1.53 fold higher than the production rate over the 3% In{sub 2}O{sub 3}/TiO{sub 2} and 5 times the amount produced over the pure TiO{sub 2}. In addition, Cu was found to promote efficient production of CH{sub 3}OH and yield rate reached to 68 μmol g{sup −1} h{sup −1} over 1% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H{sub 2} reductant was less favorable for CH{sub 4} production, yet a significant amount of CH{sub 4} and CH{sub 3}OH were obtained using a mixture of H{sub 2}O/H{sub 2} reductant. Therefore, Cu-loaded In{sub 2}O{sub 3}/TiO{sub 2} catalyst has shown to be capable for