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

PubMed

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

2005-03-10

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

H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations.

PubMed

Cappelletti, David; Bartocci, Alessio; Frati, Federica; Roncaratti, Luiz F; Belpassi, Leonardo; Tarantelli, Francesco; Lakshmi, Prabha Aiswarya; Arunan, Elangannan; Pirani, Fernando

2015-11-11

New molecular beam scattering experiments have been performed to measure the total (elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as 'hydrogen bonded'.

Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluids

NASA Astrophysics Data System (ADS)

Bray, C. J.; Spooner, E. T. C.

1992-01-01

Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated (~105°C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10' × 1/8″: 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp), and off-line digital peak processing. In order of retention time these volatile peaks are: N 2, Ar, CO, CH 4, CO 2, C 2H 4, C 2H 6, C 2H 2, COS, C 3H 6, C 3H 8, C 3H 4 (propyne), H 2O (22.7 min at 80°C), SO 2, ± iso- C4H10 ± C4H8 (1-butene) ± CH3SH, C 4H 8 (iso-butylene), (?) C 4H 6 (1,3 butadiene) and ± n- C4H10 ± C4H8 (trans-2-butene) (80 and -70°C temperature programme conditions combined). H 2O is analysed directly. O 2 can be analysed cryogenically between N 2 and Ar, but has not been detected in natural samples to date in this study. H 2S, SO 2, NH 3, HCl, HCN, and H 2 ca nnot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800-900°C/4 h) are zero for 80°C temperature programme conditions, except for a large, unidentified peak at ~64 min, but contain H 2O, CO 2, and some low molecular weight hydrocarbons at -70°C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ~30 ppm molar in inclusions; PID detection limits are ~ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g., ~0.2 ppm for C 2H 4; ~ 1 ppb for C 2H 2; ~0.3 ppb for C 3H 6). Precisions (1σ) are ~ ±1-2% and ~ ± 13% for H 2O in terms of total moles detected; the latter value is equivalent to ±0.6 mol% at the 95 mol% H 2O level. Major fluid inclusion volatile species have been successfully analysed on a ~50 mg fluid inclusion section chip (~7 mm × ~10 mm × ~100 μm). Initial inclusion volatile analyses of fluids of interpreted magmatic origin from

Co-processing CH4 and oxygenates on Mo/H-ZSM-5: 2. CH4-CO2 and CH4-HCOOH mixtures.

PubMed

Bedard, Jeremy; Hong, Do-Young; Bhan, Aditya

2013-08-07

Co-processing of formic acid or carbon dioxide with CH4 (FA/CH4 = 0.01-0.03 and CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 catalysts at 950 K with the prospect of kinetically coupling dehydrogenation and deoxygenation cycles results instead in a two-zone, staged bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. The addition of an oxygenate co-feed (oxygenate/CH4 = 0.01-0.03) causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unaffected by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH4 DHA. All effects of co-processing oxygenates with CH4 can be construed in terms of an approach to equilibrium.

Isolation and structures of sulfonium salts derived from thioethers: [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)].

PubMed

Jura, Marek; Levason, William; Reid, Gillian; Webster, Michael

2009-10-07

Two very unusual sulfonium salts, [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)], obtained from reaction of the thioethers with NbF(5) in CH(2)Cl(2) solution, are reported and their structures described; the eight-coordinate tetrafluoro Nb(v) cation of the dithioether is obtained from the same reaction.

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Surface modification of layered perovskite Sr2TiO4 for improved CO2 photoreduction with H2O to CH4.

PubMed

Kwak, Byeong Sub; Do, Jeong Yeon; Park, No-Kuk; Kang, Misook

2017-11-27

Layered perovskite Sr 2 TiO 4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr 2 TiO 4 , and thus to improve its photocatalytic activity for CO 2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N 2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO 2 photoreduction was performed in a closed reactor under 6 W/cm 2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr 2 TiO 4 catalyst (E-Sr 2 TiO 4 ) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr 2 TiO 4 photocatalyst showed an excellent catalytic performance for CO 2 photoreduction reaction. The rate of CH 4 production from the photoreduction of CO 2 with H 2 O using E-Sr 2 TiO 4 was about 3431.77 μmol/g cat after 8 h.

Synthesis and structure of cesium complexes of nitrilotris(methylenephosphonic) acid [Cs-μ6-NH(CH2PO3)3H4] and [Cs2-μ10-NH(CH2PO3H)3] · H2O

NASA Astrophysics Data System (ADS)

Somov, N. V.; Chausov, F. F.; Zakirov, R. M.

2017-07-01

3D coordination polymers cesium nitrilotris(methylenephosphonate) and dicesium nitrilotris( methylenephosphonate) are synthesized and their crystal structure is determined. In the crystal of [Cs-μ6-NH(CH2PO3)3H4] (space group P, Z = 2), cesium atoms occupy two crystallographically inequivalent positions with c.n. = 10 and c.n. = 14. The phosphonate ligand plays the bridging function; its denticity is nine. The crystal packing consists of alternating layers of Cs atoms in different environments with layers of ligand molecules between them. A ligand is bound to three Cs atoms of one layer and three Cs atoms of another layer. In the crystal of [Cs2-μ10-NH(CH2PO3H)3] · H2O (space group P, Z = 2), the complex has a dimeric structure: the bridging phosphonate ligand coordinates Cs to form a three-dimensional Cs4O6 cluster. The denticity of the ligand is equal to nine; the coordination numbers of cesium atoms are seven and nine. Two-dimensional corrugated layers of Cs4O6 clusters lie in the (002) plane, and layers of ligand molecules are located between them. Each ligand molecule coordinates eight Cs atoms of one layer and two Cs atoms of the neighboring layer.

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H]0/+ species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H-, F- and Cl-) and their [Ru(R2PCH2CH2PR2)2(L)H]+ congeners.

PubMed

Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

2017-02-28

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC) 4 (L)H] 0/+ species (NHC = N-heterocyclic carbene; L = vacant, H 2 , N 2 , CO, MeCN, O 2 , P 4 , SO 2 , H - , F - and Cl - ), as well as selected phosphine analogues [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 (L)H] + (R = i Pr, Cy; L = vacant, O 2 ). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl - , F - ) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru d π orbitals and the unoccupied σ* Ru-H orbital. In [Ru(NHC) 4 (η 2 -O 2 )H] + a δ-interaction with the O 2 ligand results in a low-lying LUMO of d π character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) d π orbital under the L z angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru( i Pr 2 PCH 2 CH 2 P i Pr 2 ) 2 (η 2 -O 2 )H] + (δ = -6.2 ppm) and [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 H] + (ca. -32 ppm, R = i Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC) 4 H] + analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily

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

USGS Publications Warehouse

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 supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

PubMed

Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

2003-06-11

Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

A V(IV) Hydroxyhydrogenomonophosphate with an Intersecting Tunnel Structure: HK 4[V 10O 10(H 2O) 2(OH) 4(PO 4) 7]·9H 2O

NASA Astrophysics Data System (ADS)

Berrah, F.; Guesdon, A.; Leclaire, A.; Borel, M. M.; Provost, J.; Raveau, B.

1999-12-01

A V(IV) hydroxyhydrogenomonophosphate HK4[V10O10(H2O)2(OH)4(PO4)7]·9H2O has been obtained, using hydrothermal conditions. Its structure, closely related to that of (CH3)2NH2K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O, differs from the latter by its I41/a space group (instead of P43). This difference corresponds to a "disordering" of the vanadium atoms, with respect to the dimethyl ammonium phase. It is shown that this disorder, which appears in the form of "V5O22" units distributed at random, does not affect the oxygen framework. The analysis of this complex structure shows that it can be described from the stacking along c of [V8P7O38(OH)4(H2O)2]∞ layers interconnected through layers of isolated VO6 octahedra. In this structure, built up of VO6, VO5OH, and VO4(OH)(H2O) octahedra, of VO4OH pyramids, and of PO4 tetrahedra, large "toffee" tunnels and smaller ones with a tulip-shape section are running along a (or b). The first ones are stuffed with H2O molecules forming aquo tubes, where protons are likely "delocalized," whereas the second ones are occupied by K+ cations.

Collision efficiency of water in the unimolecular reaction CH4 (+H2O) ⇆ CH3 + H (+H2O): one-dimensional and two-dimensional solutions of the low-pressure-limit master equation.

PubMed

Jasper, Ahren W; Miller, James A; Klippenstein, Stephen J

2013-11-27

The low-pressure-limit unimolecular decomposition of methane, CH4 (+M) ⇆ CH3 + H (+M), is characterized via low-order moments of the total energy, E, and angular momentum, J, transferred due to collisions. The low-order moments are calculated using ensembles of classical trajectories, with new direct dynamics results for M = H2O and new results for M = O2 compared with previous results for several typical atomic (M = He, Ne, Ar, Kr) and diatomic (M = H2 and N2) bath gases and one polyatomic bath gas, M = CH4. The calculated moments are used to parametrize three different models of the energy transfer function, from which low-pressure-limit rate coefficients for dissociation, k0, are calculated. Both one-dimensional and two-dimensional collisional energy transfer models are considered. The collision efficiency for M = H2O relative to the other bath gases (defined as the ratio of low-pressure limit rate coefficients) is found to depend on temperature, with, e.g., k0(H2O)/k0(Ar) = 7 at 2000 K but only 3 at 300 K. We also consider the rotational collision efficiency of the various baths. Water is the only bath gas found to fully equilibrate rotations, and only at temperatures below 1000 K. At elevated temperatures, the kinetic effect of "weak-collider-in-J" collisions is found to be small. At room temperature, however, the use of an explicitly two-dimensional master equation model that includes weak-collider-in-J effects predicts smaller rate coefficients by 50% relative to the use of a statistical model for rotations. The accuracies of several methods for predicting relative collision efficiencies that do not require solving the master equation and that are based on the calculated low-order moments are tested. Troe's weak collider efficiency, βc, includes the effect of saturation of collision outcomes above threshold and accurately predicts the relative collision efficiencies of the nine baths. Finally, a brief discussion is presented of mechanistic details of the

Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

PubMed

Monegan, Jessie D; Bunge, Scott D

2009-04-06

The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

NASA Astrophysics Data System (ADS)

Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

2016-04-01

The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

CW EC-QCL-based sensor for simultaneous detection of H 2O, HDO, N 2O and CH 4 using multi-pass absorption spectroscopy

DOE PAGES

Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; ...

2016-05-03

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H 2O, HDO, N 2O and CH 4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm -1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H 2O at 1281.161 cm -1, HDO at 1281.455 cm -1, N 2O at 1281.53 cm -1 and CH 4 at 1281.61 cm -1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonicmore » detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H 2O, 3.92 ppbv for HDO, 1.43 ppbv for N 2O, and 2.2 ppbv for CH 4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

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

PubMed

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.

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4-CO 2-H 2O) Interactions in Shale Nanopores under Reservoir Conditions

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

Wang, Yifeng

2016-04-29

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions.

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

Wang, Yifeng

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Laboratory Studies on the Formation of Three C2H4O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C2H4O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I.

2005-11-01

Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.

In situ stratospheric measurements of CH4, (C-13)H4, N2O, and OC(O-18) using the BLISS tunable diode laser spectrometer

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; May, Randy D.

1992-01-01

Simultaneous in situ measurements of stratospheric CH4, (C-13)H4, N2O, OC(O-18), pressure, and temperature have been made from Palestine, Texas (32 deg N) in September 1988 with the JPL Balloon-borne Laser In Situ Sensor. Measurements of CH4 and N2O in the altitude range 30-35 km agree well with other measurements, except for an anomalously high value for the N2O at 31 km. Measurements of CH4 support earlier observations of fold in the vertical profile. A ratio for stratospheric (C-13)H4/CH4 of 0.0105 +/- 0.0010 implies an enrichment of delta(C-13) = -45 +/- 92 parts per thousand over the PDB value, in agreement with previous measurements in the troposphere. A large mixing ratio of 1.9 +/- 0.2 ppmv for OC(O-18) is measured, corresponding to an enrichment of delta(O-18) = 280 +/- 50 parts per thousand for the (O-18) isotopic species over the SMOW value.

ATMOS Measurements of H2O + 2CH4 and Total Reactive Nitrogen in the November 1994 Antarctic Stratosphere: Dehydration and Denitrification in the Vortex

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Gunson, M. R.; Salawitch, R. J.; Newchurch, M. J.; Zander, R.; Abbas, M. M.; Abrams, M. C.; Manney, G. L.; Michelsen, H. A.; Chang, A. Y.;

Synthesis and characterization of two novel inorganic/organic hybrid materials based on polyoxomolybdate clusters: (C5H5N5)2(C5H6N5)4[(HAsO4)2Mo6O18]·11H2O and Na2(Himi)3[SeMo6O21(CH3COO)3]·6H2O

NASA Astrophysics Data System (ADS)

Ayed, Meriem; Mestiri, Imen; Ayed, Brahim; Haddad, Amor

2017-01-01

Two new organic-inorganic hybrid compound, (C5H5N5)2(C5H6N5)4[(HAsO4)2Mo6O18]·11H2O (I) and Na2(Himi)3[SeMo6O21(CH3COO)3]·6H2O (II) were synthesized and structurally characterized by scanning electron microscopy (SEM), elemental analyses, FTIR, UV spectroscopy, thermal stability analysis, XRD and single crystal X-ray diffraction. Crystal data: (I) triclinic system, space group P-1, a = 11,217 (9) Å, b = 11,637 (8) Å, c = 14,919 (8) Å, α = 70,90 (5)°, β = 70,83 (2)°, γ = 62,00(1)° and Z = 1; (II) triclinic system, space group P-1, a = 10.6740(1) Å, b = 10.6740(1) Å, c = 20.0570(1) Å, α = 76.285(1)°, β = 82.198(2)°, γ = 87.075(1)°, Z = 1. The crystal structure of (I) can be described by infinite polyanions [(HAsO4)2Mo6O18]4- organized with water molecules in layers parallel to the c-direction; adjacent layers are further joined up by hydrogen bonding interactions with organic groups which were associated in chains spreading along the b-direction. The structure of (II) consists of functionalized selenomolybdate clusters [SeMo6O21(CH3COO)3]5-, protonated imidazole cations, sodium ions and lattice water molecules, which are held together to generate a three-dimensional supramolecular network via hydrogen-bonding interaction. Furthermore, the electrochemical properties of these compounds have been studied.

Continuous multi-plot measurements of CO2, CH4, N2O and H2O in a managed boreal forest - The importance of accounting for all greenhouse gases

NASA Astrophysics Data System (ADS)

Vestin, P.; Mölder, M.; Sundqvist, E.; Båth, A.; Lehner, I.; Weslien, P.; Klemedtsson, L.; Lindroth, A.

2015-12-01

In order to assess the effects of different management practices on the exchange of greenhouse gases (GHG), it is desirable to perform repeated and parallel measurements on both experimental and control plots. Here we demonstrate how a system system combining eddy covariance and gradient techniques can be used to perform this assessment in a managed forest ecosystem.The net effects of clear-cutting and stump harvesting on GHG fluxes were studied at the ICOS site Norunda, Sweden. Micrometeorological measurements (i.e., flux-gradient measurements in 3 m tall towers) allowed for quantification of CO2, CH4 and H2O fluxes (from May 2010) as well as N2O and H2O fluxes (from June 2011) at two stump harvested plots and two control plots. There was one wetter and one drier plot of each treatment. Air was continuously sampled at two heights in the towers and gas concentrations were analyzed for CH4, CO2, H2O (LGR DLT-100, Los Gatos Research) and N2O, H2O (QCL Mini Monitor, Aerodyne Research). Friction velocities and sensible heat fluxes were measured by sonic anemometers (Gill Windmaster, Gill Instruments Ltd). Automatic chamber measurements (CO2, CH4, H2O) were carried out in the adjacent forest stand and at the clear-cut during 2010.Average CO2 emissions for the first year ranged between 14.4-20.2 ton CO2 ha-1 yr-1. The clear-cut became waterlogged after harvest and a comparison of flux-gradient data and chamber data (from the adjacent forest stand) indicated a switch from a weak CH4 sink to a significant source at all plots. The CH4 emissions ranged between 0.8-4.5 ton CO2-eq. ha-1 yr-1. N2O emissions ranged between 0.4-2.6 ton CO2-eq. ha-1 yr-1. Enhanced N2O emission on the drier stump harvested plot was the only clear treatment effect on GHG fluxes that was observed. Mean CH4 and N2O emissions for the first year of measurements amounted up to 29% and 20% of the mean annual CO2 emissions, respectively. This highlights the importance of including all GHGs

High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

NASA Astrophysics Data System (ADS)

Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

2018-06-01

How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

Theoretical kinetics of O + C 2H 4

DOE PAGES

Li, Xiaohu; Jasper, Ahren W.; Zádor, Judit; ...

2016-06-01

The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C 2H 4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C 2Hmore » 4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C 2H 4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH 2CHO+H and CH 2+CH 2O as the major products, which differs from the room temperature preference for CH 3+HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.« less

The Dissociation Energies of CH4 and C2H2 Revisited

NASA Technical Reports Server (NTRS)

Partridge, Harry; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.

Gas-phase hydrogen atom abstraction reactions of S- with H2, CH4, and C2H6

NASA Astrophysics Data System (ADS)

Angel, Laurence A.; Dogbevia, Moses K.; Rempala, Katarzyna M.; Ervin, Kent M.

2003-11-01

Reaction cross sections, product axial velocity distributions, and potential energy surfaces are presented for the hydrogen atom abstraction reactions S-+RH→R+HS- (R=H, CH3, C2H5) as a function of collision energy. The observed threshold energy, E0, for S-+H2→H+HS- agrees with the reaction endothermicity, ΔrH0. At low collision energies, the H+HS- products exhibit symmetric, low-recoil-velocity scattering, consistent with statistical reaction behavior. The S-+CH4→CH3+HS- and S-+C2H6→C2H5+HS reactions, in contrast, show large excess threshold energies when compared to ΔrH0. The excess energies are partly explained by a potential energy barrier separating products from reactants. However, additional dynamical constraints must account for more than half of the excess threshold energy. The observed behavior seems to be general for collisional activation of anion-molecule reactions that proceed through a tight, late transition state. For RH=CH4 and C2H6, the HS- velocity distributions show anisotropic backward scattering at low collision energies indicating small impact parameters and a direct rebound reaction mechanism. At higher collision energies, there is a transition to HS- forward scattering and high velocities consistent with grazing collisions and a stripping mechanism.

A novel Zn-based heterocycle metal-organic framework for high C2H2/C2H4, CO2/CH4 and CO2/N2 separations

NASA Astrophysics Data System (ADS)

Zhang, Ling; Jiang, Ke; Yang, Yu; Cui, Yuanjing; Chen, Banglin; Qian, Guodong

2017-11-01

Efficient separation of the small gas molecules especially the hydrocarbons is essential to social economy. The microporous metal-organic frameworks (MOFs) are taking precedence in this respect by virtue of their irreplaceable advantages. Herein, the new organic linker 5-(5-carboxypyridin-3-yl)isophthalic acid simplified as H3L-N has been excavated to construct successfully the novel Zn-based heterocycle metal-organic framework ZnL·(DMF)1.5·(H2O)6.0 (ZJU-197, ZJU = Zhejiang University, DMF = N,N-dimethylformamide). ZJU-197 has been structurally characterized and explored in details for gas separation. It is commendable that the activated ZJU-197a has exhibited excellent C2H2/C2H4, CO2/CH4 and CO2/N2 separations simultaneously with IAST selectivity of 137.8, 53.0 and 514.1 respectively at ambient conditions.

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

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

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

Tan, Ting; Yang, Xueliang; Ju, Yiguang

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

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

NASA Technical Reports Server (NTRS)

Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

1984-01-01

The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

A conjugated mess: measurements of benzene (C6H6), CH4, CO2, and H2O using a cavity ring-down spectrometer

NASA Astrophysics Data System (ADS)

Fleck, Derek; Hoffnagle, John; He, Yonggang

2017-04-01

Benzene is widely used carcinogenic chemical that ranks among the top 15 chemicals produced in the world by volume. It is part of many industrial processes from solvents to rubber and drug production and is also produced in petroleum refinement and use. OSHA and European regulators have set a strict long-term exposure limit and short-term exposure limit of 1ppm and 15ppm, respectively, to minimize hazards to a person's health. With the recent passing by the EPA of mandatory fence line monitoring of benzene at petroleum factories, it is evident that a robust, continuous measurement of benzene is necessary. Conventional measurements of benzene suffer from a high granularity (nearly 1 ppm), cumbersome sample preparation/processing, or cross-sensitivities from other gas species. The aim of this study is to show development of an analyzer using cavity ring-down spectrometry (CRDS) to measure benzene, as well as all the main constituents of air that can influence a measurement: H2O, CO2, and CH4. A measurement of benzene to an uncertainty of 100 ppb in <5 minutes is currently attainable, with a future goal of making this measurement in only ten seconds to 1 minute. Initial results show precisions of CH4 at 0.5ppb, CO2 at 0.5ppm and H2O of 10ppm. Because of the relatively IR-inactive C6H6 molecule, only broad features lying underneath the relatively sharp signals of CH4, CO2, and H2O can be used to quantify benzene concentrations. The stability of the CRDS analyzer allows us to look at structured changes in the baseline due to benzene to get out a precise measurement, while rarely having to do a zero-reference calibration. The analysis of these four species yields an instrument that is not only viable for fence line monitoring of petroleum refineries, but one that could also be used for local atmospheric monitoring of cities or even gas-stations.

Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

PubMed

Neary, Michelle C; Parkin, Gerard

2017-02-06

The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

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

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

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

2012-08-08

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

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals.

PubMed

Xu, Z F; Xu, Kun; Lin, M C

2011-04-21

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions: Quarterly Report.

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

Wang, Yifeng

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Synthetic, Infrared, 1H and 13C NMR Spectral Studies on N-(2-/3-Substituted Phenyl)-4-Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br, and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Gowda, B. Thimme; Shetty, Mahesha; Jayalakshmi, K. L.

2005-02-01

Twenty three N-(2-/3-substituted phenyl)-4-substituted benzenesulphonamides of the general formula, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br and X = CH3 or Cl have been prepared and characterized, and their infrared spectra in the solid state, 1H and 13C NMR spectra in solution were studied. The N-H stretching vibrations, νN-H, absorb in the range 3285 - 3199 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1376 - 1309 cm-1 and 1177 - 1148 cm-1, respectively. The S-N and C-N stretching vibrations absorb in the ranges 945 - 893 cm-1 and 1304 - 1168 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbons of the two benzene rings. Incremental shifts of the ring protons and carbons due to -SO2NH(2-/3-XC6H4) groups in C6H5SO2NH(2-/3-XC6H4), and 4- X'C6H4SO2- and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H5) are computed and employed to calculate the chemical shifts of the ring protons and carbons in the substituted compounds, 4-X'C6H4SO2NH(2-/3-XC6H4). The computed values agree well with the observed chemical shifts.

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

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

Neary, Michelle C.; Parkin, Gerard

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

DOE PAGES

Neary, Michelle C.; Parkin, Gerard

2017-01-19

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

Electron spin resonance of (CO 2 H)CH 2 CH 2 CH(CO 2 H) in irradiated glutaric acid

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

Horsfield, A.; Morton, J. R.; Whiffen, D. H.

It is concluded from electron spin resonance spectra that the radical (CO 2 H)CH 2 CH 2 CH(CO 2 H) remains trapped in a glutaric acid crystal after gamma -irradiation. This radical is found in two different conformations. Approximate hyperfine coupling constants are given for each, although exact interpretation is hindered by the overlapping of spectra. Reasons for the formation of the two forms of the radical are discussed.

Synthesis,and structural characterization of [(CH3(C5H4N))Ga(SCH2(CO)O)]-[(4-MepyH)]+, a novel Ga(III) five coordinate complex.

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Duraj, Stan A.; Fanwic, Phillp E.; Hepp, Aloysius F.; Martuch, Robert A.

2003-01-01

The synthesis and structural characterization of a novel ionic Ga(III) five coordinate complex [{CH3(C5H4N)}Ga(SCH2(CO)O)2]-[(4-MepyH)]+, (4-Mepy = CH3(C5H5N)) from the reaction between Ga2Cl4 with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e- bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square pyramidal geometry with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P2(sub 1)/c (No. 14) space group with a = 7.7413(6) A, b = 16.744(2) A, c = 14.459(2) A, V = 1987.1(6) A(sup 3), R(F) = 0.032 and R(sub w) = 0.038.

High Power and Frequency-Agile Optical Parametric Oscillators for Airborne DIAL Measurements of CH4 and H2O

NASA Astrophysics Data System (ADS)

Nehrir, A. R.; Shuman, T.; Chuang, T.; Hair, J. W.; Refaat, T. F.; Ismail, S.; Kooi, S. A.; Notari, A.

2014-12-01

Atmospheric methane (CH4) has the second largest radiative forcing of the long-lived greenhouse gasses (GHG) after carbon dioxide. However, methane's much shorter atmospheric lifetime and much stronger warming potential make its radiative forcing equivalent to that for CO2 over a 20-year time horizon which makes CH4 a particularly attractive target for mitigation strategies. Similar to CH4, water vapor (H2O) is the most dominant of the short-lived GHG in the atmosphere and plays a key role in many atmospheric processes. Atmospheric H2O concentrations span over four orders of magnitude from the planetary boundary layer where high impact weather initiates to lower levels in the upper troposphere and lower stratosphere (UTLS) where water vapor has significant and long term impacts on the Earth's radiation budget. NASA Langley has fostered the technology development with Fibertek, Inc. to develop frequency agile and high power (> 3 W) pulsed lasers using similar architectures in the 1645 nm and 935 nm spectral bands for DIAL measurements of CH4 and H2O, respectively. Both systems utilize high power 1 kHz pulse repetition frequency Nd:YAG lasers to generate high power laser emission at the desired wavelength via optical parametric oscillators (OPO). The CH4 OPO, currently in its final build stage in a SBIR Phase II program has demonstrated >2 W average power with injection seeding from a distributed feedback (DFB) laser during risk reduction experiments. The H2O OPO has demonstrated high power operation (>2 W) during the SBIR Phase I program while being injection seeded with a DFB laser, and is currently funded via an SBIR Phase II to build a robust system for future integration into an airborne water vapor DIAL system capable of profiling from the boundary layer up to the UTLS. Both systems have demonstrated operation with active OPO wavelength control to allow for optimization of the DIAL measurements for operation at different altitudes and geographic regions. An

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

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

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

Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

PubMed

Deville, Claire; McKee, Vickie; McKenzie, Christine J

2017-01-17

The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

NASA Technical Reports Server (NTRS)

Brown, L. R.; Toth, R. A.

1985-01-01

The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

Structural study of CH4, CO2 and H2O clusters containing from several tens to several thousands of molecules

NASA Astrophysics Data System (ADS)

Torchet, G.; Farges, J.; de Feraudy, M. F.; Raoult, B.

Clusters are produced during the free jet expansion of gaseous CH4, CO2 or H2O. For a given stagnation temperature To, the mean cluster size is easily increased by increasing the stagnation pressure p0. On the other hand, the cluster temperature does not depend on stagnation conditions but mainly on properties of the condensed gas. An electron diffraction analysis provides information about the cluster structure. Depending on whether the diffraction patterns exhibit crystalline lines or not, the structure is worked out either by using crystallographic methods or by constructing cluster models. When they contain more than a few thousand molecules, clusters show a crystalline structure identical to that of one phase, namely, the cubic phase, known in bulk solid: plastic phase (CH4), unique solid phase (CO2) or metastable cubic phase (H2O). When decreasing the cluster size, the studied compounds behave quite differently: CO2 clusters keep the same crystalline structure, CH4 clusters show the multilayer icosahedral structure wich has been found in rare gas clusters, and H2O clusters adopt a disordered structure different from the amorphous structures of bulk ice. Des agrégats sont produits au cours de la détente en jet libre des gaz CH4, CO2 ou H2O. Pour une température initiale donnée To, on accroît facilement la taille moyenne des agrégats en augmentant la pression initiale po . Par contre, la température des agrégats dépend principalement des propriétés du gaz condensé. Une analyse par diffraction électronique permet l'étude de la structure des agrégats. Selon que les diagrammes de diffraction contiennent ou non des raies cristallines, on a recours soit à des méthodes cristallographiques soit à la construction de modèles d'agrégats. Lorsqu'ils renferment plus de quelques milliers de molécules, les agrégats adoptent la structure cristalline de l'une des phases connues du solide massif et plus précisément la phase cubique : phase plastique pour

Synthesis and structure of heptaaqua(nitrilotris(methylenephosphonato))(dibarium)sodium monohydrate [Na(H{sub 2}O){sub 3}(μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(μ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O

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

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

Crystals of the monohydrate form of heptaaqua(nitrilotris(methylenephosphonato))(dibarium) sodium [Na(H{sub 2}O{sub )3}(µ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(µ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O are obtained; space group P2{sub 1}/c, Z = 4; a = 13.9117(10) Å, b = 11.54030(10) Å, and c = 24.1784(17) Å, ß = 148.785(18)°. The Na atom is coordinated octahedrally by one oxygen atom of a phosphonate group and five water molecules, including two bridging molecules. Ba atoms occupy two inequivalent crystallographic positions with coordination number eight and nine. The coordination spheres of both Ba atoms include two water molecules. Each ligand is bound to one Namore » atom and five Ba atoms forming three Ba–O–P–O and five Ba–O–P–C–N–C–P–O chelate cycles. In addition to the coordination bonds, molecules, including the solvate water molecule, are involved in hydrogen bonds in the crystal packing.« less

Synthesis, spectral and antifungal analysis of diaryldithiophosphates of mono- and dibutyltin(IV): x-ray structure of [{(3,5-CH3)2C6H3O)2PS2}2Sn(nBu)2].

PubMed

Syed, Atiya; Khajuria, Ruchi; Kumar, Sandeep; Jassal, Amanpreet Kaur; Hundal, Maninder S; Pandey, Sushil K

2014-01-01

Diaryldithiophosphate complexes of mono- and dibutyltin(IV) corresponding to [(ArO)(2)PS(2)(n)Sn(nBu)xCl(4-x-n)] (Ar = o-CH(3)C(6)H(4), m-CH(3)C(6)H(4), p-CH(3)C(6)H(4), 4-Cl-3-CH(3)C(6)H(3), (3,5-CH(3))(2)C(6)H(3); n = 1, 2 for x = 1 and n = 2 for x = 2) were successfully isolated and characterized by elemental analyses, IR, multinuclear NMR ((1)H, (13)C, (31)P and (119)Sn) spectroscopy and X-ray analysis. The thermal properties of the complex [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)Sn(nBu)(2) (12) have been examined by combined DTA/ DTG thermal analyses. Single crystal X-ray analysis of [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)S(n)(nBu)(2) (12) revealed that two diaryldithiophosphate ions are coordinated to tin atom in an anisobidentate fashion through the sulfur atoms of each dithiophosphate moiety leading to distorted skew-trapezoidal bipyramidal geometry. The antifungal activity depicts that these complexes are active against fungus Penicillium chrysogenium.

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.

PubMed

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.

A new method for CH3O2 and C2H5O2 radical detection and kinetic studies of the CH3O2 self-reaction in HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

NASA Astrophysics Data System (ADS)

Onel, L. C.; Brennan, A.; Ingham, T.; Kirk, D.; Leggott, A.; Seakins, P. W.; Whalley, L.; Heard, D. E.

2016-12-01

Peroxy (RO2) radicals such as methylperoxy (CH3O2) and ethylperoxy (C2H5O2) are significant atmospheric species in the ozone formation in the presence of NO. At low concentrations of NO, the self-reaction of RO2 and RO2 + HO2 are important radical termination reactions. Despite their importance, at present typically only the sum of RO2 is measured in the atmosphere, making no distinction between different RO2 species.A new method has been developed for the direct detection of CH3O2 and C2H5O2 by FAGE (Fluorescence Assay by Gas Expansion) by titrating the peroxy radicals to RO (R = CH3 and C2H5) by reaction with NO and then detecting the resultant RO by laser induced fluorescence. The method has the potential to directly measure atmospheric levels of CH3O2 and potentially other RO2 species. The limit of detection is 3.8 × 108 molecule cm-3 for CH3O2 and 4.9 × 109 molecule cm-3 for C2H5O2 for a signal-to-noise ratio of 2 and a 4 min averaging time. The method has been used for time-resolved monitoring of CH3O2 during its self-reaction within HIRAC at 1 bar and at room temperature to determine a rate coefficient that is lower than the range of the previous results obtained by UV absorption measurements (http://iupac.pole-ether.fr/). A range of products of the CH3O2 self-reaction were also observed for the two reaction channels, (a) leading to formaldehyde and methanol and (b) forming methoxy (CH3O) radicals, over a range of temperatures from 296 - 340 K: CH3O and HO2 radicals (from reaction of CH3O + O2) were monitored by FAGE, formaldehyde was measured by FAGE and FTIR, and methanol was observed by FTIR. Good agreement was observed between the FTIR and FAGE measurements of formaldehyde. Using the concentrations of methanol and formaldehyde, the branching ratios at room temperature have been determined and are in very good agreement with the values recommended by IUPAC. Little temperature dependence of the branching ratios has been observed from 296 K to 340 K.

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

PubMed

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

2014-11-26

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

A flux-gradient system for simultaneous measurement of the CH4, CO2, and H2O fluxes at a lake-air interface.

PubMed

Xiao, Wei; Liu, Shoudong; Li, Hanchao; Xiao, Qitao; Wang, Wei; Hu, Zhenghua; Hu, Cheng; Gao, Yunqiu; Shen, Jing; Zhao, Xiaoyan; Zhang, Mi; Lee, Xuhui

2014-12-16

Inland lakes play important roles in water and greenhouse gas cycling in the environment. This study aims to test the performance of a flux-gradient system for simultaneous measurement of the fluxes of water vapor, CO2, and CH4 at a lake-air interface. The concentration gradients over the water surface were measured with an analyzer based on the wavelength-scanned cavity ring-down spectroscopy technology, and the eddy diffusivity was measured with a sonic anemometer. Results of a zero-gradient test indicate a flux measurement precision of 4.8 W m(-2) for water vapor, 0.010 mg m(-2) s(-1) for CO2, and 0.029 μg m(-2) s(-1) for CH4. During the 620 day measurement period, 97%, 69%, and 67% of H2O, CO2, and CH4 hourly fluxes were higher in magnitude than the measurement precision, which confirms that the flux-gradient system had adequate precision for the measurement of the lake-air exchanges. This study illustrates four strengths of the flux-gradient method: (1) the ability to simultaneously measure the flux of H2O, CO2, and CH4; (2) negligibly small density corrections; (3) the ability to resolve small CH4 gradient and flux; and (4) continuous and noninvasive operation. The annual mean CH4 flux (1.8 g CH4 m(-2) year(-1)) at this hypereutrophic lake was close to the median value for inland lakes in the world (1.6 g CH4 m(-2) year(-1)). The system has adequate precision for CH4 flux for broad applications but requires further improvement to resolve small CO2 flux in many lakes.

Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

PubMed Central

Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

2010-01-01

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

The NASA Langley High Altitude Lidar Observatory (HALO) - Advancements in Airborne DIAL Measurements of CH4 and H2O

NASA Astrophysics Data System (ADS)

Nehrir, A. R.; Hair, J. W.; Ferrare, R. A.; Hostetler, C. A.; Notari, A.; Collins, J. E., Jr.; Hare, R. J.; Harper, D. B.; Antill, C.; Cook, A. L.; Young, J.; Chuang, T.; Welch, W.

2016-12-01

Atmospheric methane (CH4) has the second largest radiative forcing of the long-lived greenhouse gasses (GHG) after carbon dioxide. However, methane's much shorter atmospheric lifetime and much stronger warming potential make its radiative forcing equivalent to that for CO2 over a 20-year time horizon which makes CH4 a particularly attractive target for mitigation strategies. Similar to CH4, water vapor (H2O) is the most dominant of the short-lived GHG in the atmosphere and plays a key role in many atmospheric processes. Atmospheric H2O concentrations span over four orders of magnitude from the planetary boundary layer where high impact weather initiates to lower levels in the upper troposphere and lower stratosphere where water vapor has significant and long term impacts on the Earth's radiation budget. Active remote sensing employing the differential absorption lidar (DIAL) technique enables scientific assessments of both natural and anthropogenic sources and sinks of CH4 with high accuracy and precision as well as and its impacts on the climate. The DIAL technique also allows for profiling of tropospheric water vapor for weather and climate applications with unprecedented spatial and temporal resolution. NASA Langley is developing the High Altitude Lidar Observatory (HALO) lidar system to address the observational needs of NASA's weather, climate, carbon cycle, and atmospheric composition focus areas. HALO is a multi-function airborne lidar being developed to measure atmospheric H2O and CH4 mixing ratios and aerosol and cloud optical properties using the DIAL and High Spectral Resolution Lidar (HSRL) techniques, respectively. HALO is designed as an airborne simulator for future space based DIAL missions and will serve as test bed for risk reduction of key technologies required of future space based GHG DIAL missions. A system level overview and up-to-date progress of the HALO lidar will be presented. Simulations on the expected accuracy and precision of HALO CH4

Seasonal Variations of Water Vapor in the Lower Stratosphere Inferred from ATMOS/ATLAS-3 Measurements of H2O and CH4

NASA Technical Reports Server (NTRS)

Abbas, M. M.; Michelsen, H. A.; Gunson, M. R.; Abrams, M. C.; Newchurch, M. J.; Salawitch, R. J.; Chang, A. Y.; Goldman, A.; Irion, F. W.; Manney, G. L.;

Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets).

PubMed

Holm, N G; Oze, C; Mousis, O; Waite, J H; Guilbert-Lepoutre, A

2015-07-01

Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds.

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere.

PubMed

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

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(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(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, 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(3)SO(3)) (P1, 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)°, 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(3)SO(3)] ions. V(2)O(3)(CH(3)SO(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(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(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(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(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(2)O(5) are formed. Copyright �

On the Formation of the C2H6O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I.

2017-06-01

The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

Biomass fast pyrolysis in a fluidized bed reactor under N2, CO2, CO, CH4 and H2 atmospheres.

PubMed

Zhang, Huiyan; Xiao, Rui; Wang, Denghui; He, Guangying; Shao, Shanshan; Zhang, Jubing; Zhong, Zhaoping

2011-03-01

Biomass fast pyrolysis is one of the most promising technologies for biomass utilization. In order to increase its economic potential, pyrolysis gas is usually recycled to serve as carrier gas. In this study, biomass fast pyrolysis was carried out in a fluidized bed reactor using various main pyrolysis gas components, namely N(2), CO(2), CO, CH(4) and H(2), as carrier gases. The atmosphere effects on product yields and oil fraction compositions were investigated. Results show that CO atmosphere gave the lowest liquid yield (49.6%) compared to highest 58.7% obtained with CH(4). CO and H(2) atmospheres converted more oxygen into CO(2) and H(2)O, respectively. GC/MS analysis of the liquid products shows that CO and CO(2) atmospheres produced less methoxy-containing compounds and more monofunctional phenols. The higher heating value of the obtained bio-oil under N(2) atmosphere is only 17.8 MJ/kg, while that under CO and H(2) atmospheres increased to 23.7 and 24.4 MJ/kg, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2011-03-01

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

Proton transfer reactions and dynamics in CH(3)OH-H(3)O(+)-H(2)O complexes.

PubMed

Sagarik, Kritsana; Chaiwongwattana, Sermsiri; Vchirawongkwin, Viwat; Prueksaaroon, Supakit

2010-01-28

Proton transfer reactions and dynamics in hydrated complexes formed from CH(3)OH, H(3)O(+) and H(2)O were studied using theoretical methods. The investigations began with searching for equilibrium structures at low hydration levels using the DFT method, from which active H-bonds in the gas phase and continuum aqueous solution were characterized and analyzed. Based on the asymmetric stretching coordinates (Deltad(DA)), four H-bond complexes were identified as potential transition states, in which the most active unit is represented by an excess proton nearly equally shared between CH(3)OH and H(2)O. These cannot be definitive due to the lack of asymmetric O-H stretching frequencies (nu(OH)) which are spectral signatures of transferring protons. Born-Oppenheimer molecular dynamics (BOMD) simulations revealed that, when the thermal energy fluctuations and dynamics were included in the model calculations, the spectral signatures at nu(OH) approximately 1000 cm(-1) appeared. In continuum aqueous solution, the H-bond complex with incomplete water coordination at charged species turned out to be the only active transition state. Based on the assumption that the thermal energy fluctuations and dynamics could temporarily break the H-bonds linking the transition state complex and water molecules in the second hydration shell, elementary reactions of proton transfer were proposed. The present study showed that, due to the coupling among various vibrational modes, the discussions on proton transfer reactions cannot be made based solely on static proton transfer potentials. Inclusion of thermal energy fluctuations and dynamics in the model calculations, as in the case of BOMD simulations, together with systematic IR spectral analyses, have been proved to be the most appropriate theoretical approaches.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

NASA Astrophysics Data System (ADS)

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

PubMed Central

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-01-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311–500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400–500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane. PMID:27666288

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures.

PubMed

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-26

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H 2 ) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H 2 /CH 4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H 2 /CH 4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H 2 /CH 4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H 2 /CH 4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H 2 /CH 4 ratios cannot reliably discriminate abiotic from biotic methane.

Mercury-Bridged Cobaltacarborane Complexes Containing B-Hg-B Three-Center Bonds. Synthesis and Structure of mu, mu’-((n5-C5R5)Co(CH3)2C2B3H4)Hg, mu-(n(5)-C5R5)Co(CH3)2C2B3H4)HgCl, (R=H, CH3) and Related Compounds.

DTIC Science & Technology

1980-11-01

MERCURY-BRIDGED COBALTACARBORANE COMPLEXES CONTAINING B-HG-B TH--ETC(U) NOV 80 D C FINSTER . R N GRIMES N0 0 0 1 4-75-0305 UNCLASSXFIED TR󈧨 NL ILn...C5R5) Co 3)2C2B3 4 2 5 .- -C5R5 )Co(CH3)2C2B3H4 ]HgCl, (R=H, CH3 ) and Related Compounds, David C./ Finster -- Russell N./Grimes ( Department of Chemistry...Compounds 1 \\David C. Finster And Russell N. Grimes* Abstract. Reactions of the nid~p-cobaltacarborane anions 01CR )(C 3 )C BH and [n (H 1oC ihH~5n 5

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

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

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

Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets)

PubMed Central

Oze, C.; Mousis, O.; Waite, J.H.; Guilbert-Lepoutre, A.

2015-01-01

Abstract Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds. Key Words: Serpentinization—Fischer-Tropsch-type synthesis—Hydrogen formation—Methane formation—Ultramafic rocks. Astrobiology 15, 587–600. PMID:26154779

Synthetic and Spectroscopic Studies on N-(i,j-Disubstituted Phenyl)-4- Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i, j = 2, 3; 2, 4; 2, 5; 2, 6 or 3, 4; and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Shetty, Mahesha; Gowda, B. Thimme

2005-02-01

Fifty four N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides of the general formula 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i,j = 2,3; 2,4; 2,5; 2,6 or 3, 4; and X = CH3 or Cl, are prepared and characterized and their infrared, 1H and 13C NMR spectra in solution are studied. The N-H stretching vibrations νN-H absorb in the range 3305 - 3205 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1377 - 1307 cm-1 and 1184 - 1128 cm-1, respectively. The N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides show C-S, S-N and C-N stretching vibrations in the ranges 844 - 800 cm-1, 945 - 891 cm-1 and 1309 - 1170 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of 2.jpg" /> are assigned to protons and carbon atoms of the two benzene rings. Incremental shifts of the ring protons and carbon atoms due to -SO2NH(i,j-X2C6H3) groups in C6H5SO2NH(i,j-X2C6H3) and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H*) are computed and employed to calculate the chemical shifts of the ring protons and carbon atoms in the substituted compounds 4-X'C6H4SO2NH(i,j-X2C6H3). The different methods of calculation lead to almost the same values in most cases and agree well with the observed chemical shifts, indicating the validity of the principle of additivity of the substituent effects with chemical shifts in these compounds.

Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

NASA Technical Reports Server (NTRS)

Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy

2007-01-01

Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

NASA Technical Reports Server (NTRS)

Woon, David E.

2006-01-01

While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

Solid state coordination chemistry: structural consequences of variations in tether length in the oxovanadium-copper-bisterpy-[O3P(CH2)nPO3]4- system, n= 1-6 (bisterpy = 2,2':4',4'':2'',2'''-quarterpyridyl-6',6''-di-2-pyridine).

PubMed

Ouellette, Wayne; Koo, Bon-Kweon; Burkholder, Eric; Golub, Vladimir; O'Connor, C J; Zubieta, Jon

2004-05-21

Hydrothermal reactions of Na3VO4, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2 (n = 1-6) yielded a family of materials of the type [Cu2(bisterpy)]4+/VxOy(n-)/[O3P(CH2)nPO3]4-. This family of bimetallic oxides is characterized by an unusual structural diversity. The oxides [[Cu2(bisterpy)]V2O4[O3PCH2PO3H]2] (1), [[Cu2(bisterpy)(H2O)]VO2[O3P(CH2)3PO3][HO3P(CH2)3PO3H2

Reduced gas seepages in ophiolitic complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

NASA Astrophysics Data System (ADS)

Vacquand, Christèle; Deville, Eric; Beaumont, Valérie; Guyot, François; Sissmann, Olivier; Pillot, Daniel; Arcilla, Carlo; Prinzhofer, Alain

2018-02-01

This paper proposes a comparative study of reduced gas seepages occurring in ultrabasic to basic rocks outcropping in ophiolitic complexes based on the study of seepages from Oman, the Philippines, Turkey and New Caledonia. This study is based on analyses of the gas chemical composition, noble gases contents, stable isotopes of carbon, hydrogen and nitrogen. These seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct types of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These types are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich type, associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 types. H2-bearing gases are either associated with ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and alkaline conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4. The N2-rich type is notably associated with relatively high contents of crustal 4He and in this gas type N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

CW EC-QCL-based sensor for simultaneous detection of H₂O, HDO, N₂O and CH₄ using multi-pass absorption spectroscopy.

PubMed

Yu, Yajun; Sanchez, Nancy P; Griffin, Robert J; Tittel, Frank K

2016-05-16

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H₂O, HDO, N₂O and CH₄ using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm^-1 operating at ~7.8 µm was scanned covering four neighboring absorption lines, for H₂O at 1281.161 cm^-1, HDO at 1281.455 cm^-1, N₂O at 1281.53 cm^-1 and CH₄ at 1281.61 cm^-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H₂O, 3.92 ppbv for HDO, 1.43 ppbv for N₂O, and 2.2 ppbv for CH₄ were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. Experimental measurements of ambient air are also reported.

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

PubMed Central

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

Theoretical study of geometry relaxation following core excitation: H2O, NH3, and CH4

NASA Astrophysics Data System (ADS)

Takahashi, Osamu; Kunitake, Naoto; Takaki, Saya

2015-10-01

Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H2O, NH3, and CH4 have been performed to examine geometry relaxation after core excitation. We observed faster X-H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).

Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

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

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

2009-03-15

Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

Reduced gas seepages in serpentinized peridotite complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

NASA Astrophysics Data System (ADS)

Deville, E.; Vacquand, C.; Beaumont, V.; Francois, G.; Sissmann, O.; Pillot, D.; Arcilla, C. A.; Prinzhofer, A.

2017-12-01

A comparative study of reduced gas seepages associated to serpentinized ultrabasic rocks was conducted in the ophiolitic complexes of Oman, the Philippines, Turkey and New Caledonia. This study is based on analyzes of the gas chemical composition, noble gases contents, and stable isotopes of carbon, hydrogen and nitrogen. These gas seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct families of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These families are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich family associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 families. H2-bearing gases are either associated to ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and high pH conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4 (conditions of strong carbon restriction). The N2-rich family is associated with relatively high contents of crustal 4He. In this family N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

Investigation of hydrate formation in the system H2-CH4-H2O at a pressure up to 250 MPa.

PubMed

Skiba, Sergei S; Larionov, Eduard G; Manakov, Andrey Y; Kolesov, Boris A; Kosyakov, Viktor I

2007-09-27

Phase equilibria in the system H2-CH4-H2O are investigated by means of differential thermal analysis within hydrogen concentration range 0-70 mol % and at a pressure up to 250 MPa. All the experiments were carried out under the conditions of gas excess. With an increase in hydrogen concentration in the initial gas mixture, decomposition temperature of the formed hydrates decreased. X-ray diffraction patterns and Raman spectra of the quenched hydrate samples obtained at a pressure of 20 MPA from a gas mixture containing 40 mol % hydrogen were recorded. It turned out that the hydrate has cubic structure I under these conditions. The Raman spectra showed that hydrogen molecules are not detected in the hydrate within the sensitivity of the method, that is, almost pure methane hydrate is formed. The general view of the phase diagram of the investigated system is proposed. A thermodynamic model was proposed to explain a decrease in hydrate decomposition temperature in the system with an increase in the concentration of hydrogen in the initial mixture.

(C6N2H16)[Co(H2O)6](SO4)2.2H2O: A new hybrid material based on sulfate templated by diprotonated trans-1,4-diaminocyclohexane

NASA Astrophysics Data System (ADS)

Hamdi, N.; Ngopoh, F. A. I.; da Silva, I.; El Bali, B.; Lachkar, M.

2018-03-01

Employing trans-1,4-diaminocyclohexane (DACH) as template, the new hybrid sulphate (C6N2H16)[Co(H2O)6](SO4)2.2H2O was prepared in solution. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic system (S.G.: P 21/n), with the following unit-cell parameters (Å,°): a = 6.2897(2), b = 12.3716(6), c = 13.1996(4), β = 98.091(3) V = 1016.89(7) Å3, Z = 4. Its 3D crystal structure is made upon isolated [Co(H2O)6] octahedra, regular [SO4] tetrahedra, protonated DACH and free H2O molecules, which interact through N-H···O and O-H···O hydrogen bonds. The Fourier transform infrared result exhibits bands corresponding to the vibrations of DACH, sulfate group and water molecules. The thermal decomposition of the phase consists mainly in the loss of the organic moiety and one sulfate group, leading thus to the formation of anhydrous cobalt sulfate.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Flowing afterglow studies of the electron recombination of protonated cyanides (RCN)H+ and their proton-bound dimer ions (RCN)2H+ where R is H, CH3, and CH3CH2

NASA Astrophysics Data System (ADS)

McLain, J. L.; Molek, C. D.; , D. Osborne, Jr.; Adams, N. G.

2009-05-01

A study has been made of the electron-ion dissociative recombination of the protonated cyanides (RCNH+, R = H, CH3, C2H5) and their proton-bound dimers (RCN)2H+ at 300 K. This has been accomplished with the flowing afterglow technique using an electrostatic Langmuir probe to determine the electron density decay along the flow tube. For the protonated species, the recombination coefficients, [alpha]e(cm3 s-1), are (3.6 +/- 0.5) × 10-7, (3.4 +/- 0.5) × 10-7, (4.6 +/- 0.7) × 10-7 for R = H, CH3, C2H5, respectively. For the proton-bound dimers, the [alpha]e are substantially greater being (2.4 +/- 0.4) × 10-6, (2.8 +/- 0.4) × 10-6, (2.3 +/- 0.3) × 10-6 for R = H, CH3, C2H5, respectively. Fitting of the electron density decay data to a simple model has shown that the rate coefficients for the three-body association of RCNH+ with RCN are very large being (2.0 +/- 0.5) × 10-26 cm6 s-1. The significance of these data to the Titan ionosphere is discussed.

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

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

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

Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

NASA Astrophysics Data System (ADS)

Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

Synthesis of opioidmimetics, 3-[H-Dmt-NH(CH(2))(m)]-6-[H-Dmt-NH(CH(2))(n)]-2(1H)-pyrazinones, and studies on structure-activity relationships.

PubMed

Shiotani, Kimitaka; Miyazaki, Anna; Li, Tingyou; Tsuda, Yuko; Yokoi, Toshio; Ambo, Akihiro; Sasaki, Yusuke; Bryant, Sharon D; Jinsmaa, Yunden; Lazarus, Lawrence H; Okada, Yoshio

2007-11-01

Opioidmimetics containing 3-[H-Dmt-NH-(CH(2))(m)]-6-[H-Dmt-NH-(CH(2))(n)]-2(1H)-pyrazinone symmetric (m = n, 1-4) (1 - 4) and asymmetric (m, n = 1 - 4) aliphatic chains (5 - 16) were synthesized using dipeptidyl chloromethylketone intermediates. They had high mu-affinity (K(i)mu = 0.021 - 2.94 nM), delta-affinity (K(i)delta = 1.06 - 152.6 nM), and mu selectivity (K(i)delta/K(i)mu = 14 - 3,126). The opioidmimetics (1 - 16) exhibited mu agonism in proportion to their mu-receptor affinity. delta-Agonism was essentially lacking in the compounds except (4) and (16), and (1) and (2) indicated weak delta antagonism (pA(2) = 6.47 and 6.56, respectively). The data verify that a specific length of aliphatic linker is required between the Dmt pharmacophore and the pyrazinone ring to produce unique mu-opioid receptor ligands.

Prediction of the PVTx and VLE properties of natural gases with a general Helmholtz equation of state. Part I: Application to the CH4-C2H6-C3H8-CO2-N2 system

NASA Astrophysics Data System (ADS)

Mao, Shide; Lü, Mengxin; Shi, Zeming

2017-12-01

A general equation of state (EOS) explicit in Helmholtz free energy has been developed to predict the pressure-volume-temperature-composition (PVTx) and vapor-liquid equilibrium (VLE) properties of the CH4-C2H6-C3H8-CO2-N2 fluid mixtures (main components of natural gases). This EOS, which is a function of temperature, density and composition, with four mixing parameters used, is based on the improved EOS of Sun and Ely (2004) for the pure components (CH4, C2H6, C3H8, CO2 and N2) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with the experimental data available indicates that the EOS can calculate the PVTx and VLE properties of the CH4-C2H6-C3H8-CO2-N2 fluid mixtures within or close to experimental uncertainties up to 623 K and 1000 bar within full range of composition. Isochores of the CH4-C2H6-C3H8-CO2-N2 system can be directly calculated from this EOS to interpret the corresponding microthermometric and Raman analysis data of fluid inclusions. The general EOS can calculate other thermodynamic properties if the ideal Helmholtz free energy of fluids is combined, and can also be extended to the multi-component natural gases including the secondary alkanes (carbon number above three) and none-alkane components such as H2S, SO2, O2, CO, Ar and H2O. This part of work will be finished in the near future.

Vibrational spectra of Mg2KH(XO4)2·15H2O (X = P, As) containing dimer units [H(XO4)2

NASA Astrophysics Data System (ADS)

Stefov, V.; Koleva, V.; Najdoski, M.; Abdija, Z.; Cahil, A.; Šoptrajanov, B.

2017-08-01

Infrared and Raman spectra of Mg2KH(PO4)2·15H2O and Mg2KH(AsO4)2·15H2O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg2KH(XO4)2·15H2O (X = P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO4)2] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C1 crystallographic symmetry of the XO4 groups. The observation of a singlet Raman band for the ν1(XO4) mode as well as the absence of substantial splitting of the ν3(XO4) modes and IR activation of the ν1(XO4) mode suggest that the dimer units [H(XO4)2] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg2KH(AsO4)2·15H2O, both ν1(AsО4) and ν3(AsО4) modes have practically the same wavenumber around 830 cm- 1. It was also established that the ν4(PО4) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D2O librations. As a whole, the spectral picture of Mg2KH(XO4)2·15H2O (X = P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO4·6H2O (X = P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO4)2] play a relatively small part in the general spectral appearance.

Syntheses and characterization of phosphonates and diphosphonates of molybdenum, A4[(MoO3)5(O3PR)2]·xH2O, A2[Mo2O5(O3PR)2] and A2[Mo2O5(O3P-R-PO3)] (A = K, Rb, Cs, Tl, NH4).

PubMed

Elias Jesu Packiam, D; Vidyasagar, Kanamaluru

2017-11-28

Twenty new molybdenum phosphonates and diphosphonates have been synthesized and structurally characterized by single crystal and powder X-ray diffraction, CHN analyses, spectroscopic and thermal studies. Four of them are molecular phenyl- and benzyl-phosphonates containing discrete [(MoO 3 ) 5 (O 3 PR) 2 ] 4- (R = Ph or CH 2 Ph) cyclic anions. The sixteen non-molecular compounds are layered isostructural phenylphosphonates, A 2 [Mo 2 O 5 (O 3 PPh) 2 ] (A = NH 4 , Tl, Rb, Cs) and K 1.5 (H 3 O) 0.5 [Mo 2 O 5 (O 3 PPh) 2 ] and the corresponding diphosphonate compounds with pillared anionic layers, A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 3 PO 3 )], A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 4 PO 3 )] and A 2 [Mo 2 O 5 (O 3 P(C 6 H 4 )PO 3 )]. The A + ions reside in the interlayer region as well as in the cavities within the anionic layers.

Evolution of CO2, CH4, and OCS abundances relative to H2O in the coma of comet 67P around perihelion from Rosetta/VIRTIS-H observations

NASA Astrophysics Data System (ADS)

Bockelée-Morvan, Dominique; Crovisier, J.; Erard, S.; Capaccioni, F.; Leyrat, C.; Filacchione, G.; Drossart, P.; Encrenaz, T.; Biver, N.; de Sanctis, M.-C.; Schmitt, B.; Kührt, E.; Capria, M.-T.; Combes, M.; Combi, M.; Fougere, N.; Arnold, G.; Fink, U.; Ip, W.; Migliorini, A.; Piccioni, G.; Tozzi, G.

2016-11-01

Infrared observations of the coma of 67P/Churyumov-Gerasimenko were carried out from 2015 July to September, I.e. around perihelion (2015 August 13), with the high-resolution channel of the Visible and Infrared Thermal Imaging Spectrometer instrument onboard Rosetta. We present the analysis of fluorescence emission lines of H2O, CO2, 13CO2, OCS, and CH4 detected in limb sounding with the field of view at 2.7-5 km from the comet centre. Measurements are sampling outgassing from the illuminated Southern hemisphere, as revealed by H2O and CO2 raster maps, which show anisotropic distributions, aligned along the projected rotation axis. An abrupt increase of water production is observed 6 d after perihelion. In the meantime, CO2, CH4, and OCS abundances relative to water increased by a factor of 2 to reach mean values of 32, 0.47, and 0.18 per cent, respectively, averaging post-perihelion data. We interpret these changes as resulting from the erosion of volatile-poor surface layers. Sustained dust ablation due to the sublimation of water ice maintained volatile-rich layers near the surface until at least the end of the considered period, as expected for low thermal inertia surface layers. The large abundance measured for CO2 should be representative of the 67P nucleus original composition, and indicates that 67P is a CO2-rich comet. Comparison with abundance ratios measured in the Northern hemisphere shows that seasons play an important role in comet outgassing. The low CO2/H2O values measured above the illuminated Northern hemisphere are not original, but the result of the devolatilization of the uppermost layers.

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

Co3(PO4)2·4H2O

PubMed Central

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

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

PubMed

Loeffler, Mark J; Hudson, Reggie L

2015-06-01

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

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

NASA Technical Reports Server (NTRS)

Loeffler, Mark Josiah; Hudson, Reggie Lester

2015-01-01

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

Unimolecular reactivity of organotrifluoroborate anions, RBF3- , and their alkali metal cluster ions, M(RBF3 )2- (M = Na, K; R = CH3 , CH3 CH2 , CH3 (CH2 )3 , CH3 (CH2 )5 , c-C3 H5 , C6 H5 , C6 H5 CH2 , CH2 CHCH2 , CH2 CH, C6 H5 CO).

PubMed

Bathie, Fiona L B; Bowen, Chris J; Hutton, Craig A; O'Hair, Richard A J

2018-07-15

Potassium organotrifluoroborates (RBF 3 K) are important reagents used in organic synthesis. Although mass spectrometry is commonly used to confirm their molecular formulae, the gas-phase fragmentation reactions of organotrifluoroborates and their alkali metal cluster ions have not been previously reported. Negative-ion mode electrospray ionization (ESI) together with collision-induced dissociation (CID) using a triple quadrupole mass spectrometer were used to examine the fragmentation pathways for RBF 3 - (where R = CH 3 , CH 3 CH 2 , CH 3 (CH 2 ) 3 , CH 3 (CH 2 ) 5 , c-C 3 H 5 , C 6 H 5 , C 6 H 5 CH 2 , CH 2 CHCH 2 , CH 2 CH, C 6 H 5 CO) and M(RBF 3 ) 2 - (M = Na, K), while density functional theory (DFT) calculations at the M06/def2-TZVP level were used to examine the structures and energies associated with fragmentation reactions for R = Me and Ph. Upon CID, preferentially elimination of HF occurs for RBF 3 - ions for systems where R = an alkyl anion, whereas R - formation is favoured when R = a stabilized anion. At higher collision energies loss of F - and additional HF losses are sometimes observed. Upon CID of M(RBF 3 ) 2 - , formation of RBF 3 - is the preferred pathway with some fluoride transfer observed only when M = Na. The DFT-calculated relative thermochemistry for competing fragmentation pathways is consistent with the experiments. The main fragmentation pathways of RBF 3 - are HF elimination and/or R - loss. This contrasts with the fragmentation reactions of other organometallate anions, where reductive elimination, beta hydride transfer and bond homolysis are often observed. The presence of fluoride transfer upon CID of Na(RBF 3 ) 2 - but not K(RBF 3 ) 2 - is in agreement with the known fluoride affinities of Na + and K + and can be rationalized by Pearson's HSAB theory. Copyright © 2018 John Wiley & Sons, Ltd.

Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter

NASA Technical Reports Server (NTRS)

Sada, P. V.; Bjoraker, G. L.; Jennings, D. E.; McCabe, G. H.; Romani, P. N.

1998-01-01

We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. c1998 Academic Press.

Vibrational spectra of Mg2KH(XO4)2·15H2O (X=P, As) containing dimer units [H(XO4)2].

PubMed

Stefov, V; Koleva, V; Najdoski, M; Abdija, Z; Cahil, A; Šoptrajanov, B

2017-08-05

Infrared and Raman spectra of Mg 2 KH(PO 4 ) 2 ·15H 2 O and Mg 2 KH(AsO 4 ) 2 ·15H 2 O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO 4 ) 2 ] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO 4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C 1 crystallographic symmetry of the XO 4 groups. The observation of a singlet Raman band for the ν 1 (XO 4 ) mode as well as the absence of substantial splitting of the ν 3 (XO 4 ) modes and IR activation of the ν 1 (XO 4 ) mode suggest that the dimer units [H(XO 4 ) 2 ] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg 2 KH(AsO 4 ) 2 ·15H 2 O, both ν 1 (AsО 4 ) and ν 3 (AsО 4 ) modes have practically the same wavenumber around 830cm -1 . It was also established that the ν 4 (PО 4 ) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D 2 O librations. As a whole, the spectral picture of Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO 4 ·6H 2 O (X=P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO 4 ) 2 ] play a relatively small part in the general spectral appearance. Copyright © 2017 Elsevier B.V. All rights reserved.

Microwave Plasma-Activated Chemical Vapor Deposition of Nitrogen-Doped Diamond. II: CH4/N2/H2 Plasmas

PubMed Central

2016-01-01

We report a combined experimental and modeling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapor deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar, and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v = 0), CN(X, v = 0), and NH(X, v = 0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely, H atoms, CH, C2, CN, and NH radicals and triplet N2 molecules. The measurements have been reproduced and rationalized from first-principles by 2-D (r, z) coupled kinetic and transport modeling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4%, with N2 present at 1–6000 ppm, at pressure p = 150 Torr, and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns

Gas-phase evolution of Ar/H2O and Ar/CH4 dielectric barrier discharge plasmas

NASA Astrophysics Data System (ADS)

Barni, Ruggero; Riccardi, Claudia

2018-04-01

We present some experimental results of an investigation aimed to hydrogen production with atmospheric pressure plasmas, based on the use of dielectric barrier discharges, fed with a high-voltage alternating signal at frequency 30-50 kHz, in mixtures of methane or water vapor diluted in argon. The plasma gas-phase of the discharge was investigated by means of optical and electrical diagnostics. The emission spectra of the discharges was measured with a wide band spectrometer and a photosensor module, based on a photomultiplier tube. A Rogowski coil allowed to measure the electric current flowing into the circuit and a high voltage probe was employed for evaluating the voltage at the electrodes. The analysis of the signals of voltage and current shows the presence of microdischarges between the electrodes in two alternating phases during the period of oscillation of the applied voltage. The hydrogen concentration in the gaseous mixture was measured too. Besides this experimental campaign, we present also results from a numerical modeling of chemical kinetics in the gas-phase of Ar/H2O and Ar/CH4 plasmas. The simulations were conducted under conditions of single discharge to study the evolution of the system and of fixed frequency repeated discharging. In particular in Ar/H2O mixtures we could study the evolution from early atomic dissociation in the discharge, to longer time scales, when chemical reactions take place producing an increase of the density of species such as OH, H2O2 and subsequently of H and H2. The results of numerical simulations provide some insights into the evolution happening in the plasma gas-phase during the hydrogen reforming process.

Carbonate control of H2 and CH4 production in serpentinization systems at elevated P-Ts

USGS Publications Warehouse

Jones, L. Camille; Rosenbauer, Robert; Goldsmith, Jonas I.; Oze, Christopher

2010-01-01

Serpentinization of forsteritic olivine results in the inorganic synthesis of molecular hydrogen (H2) in ultramafic hydrothermal systems (e.g., mid-ocean ridge and forearc environments). Inorganic carbon in those hydrothermal systems may react with H2 to produce methane (CH4) and other hydrocarbons or react with dissolved metal ions to form carbonate minerals. Here, we report serpentinization experiments at 200°C and 300 bar demonstrating Fe2+ being incorporated into carbonates more rapidly than Fe2+ oxidation (and concomitant H2 formation) leading to diminished yields of H2 and H2-dependent CH4. In addition, carbonate formation is temporally fast in carbonate oversaturated fluids. Our results demonstrate that carbonate chemistry ultimately modulates the abiotic synthesis of both H2 and CH4 in hydrothermal ultramafic systems and that ultramafic systems present great potential for CO2-mineral sequestration.

Large hydrogen-bonded pre-nucleation (HSO4-)(H2SO4)m(H2O)k and (HSO4-)(NH3)(H2SO4)m(H2O)k clusters in the earth's atmosphere.

PubMed

Herb, Jason; Xu, Yisheng; Yu, Fangqun; Nadykto, A B

2013-01-10

The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

Coexistence of cyclic (CH3OH)2(H2O)8 heterodecamer and acyclic water trimer in the channels of silver-azelate framework

NASA Astrophysics Data System (ADS)

Luo, Geng-Geng; Zhu, Rui-Min; He, Wei-Jun; Li, Ming-Zhi; Zhao, Qing-Hua; Li, Dong-Xu; Dai, Jing-Cao

2012-08-01

Flexible azelaic acid (H2aze) and 1,3-bis(4-pyridyl)propane) (bpp) react ultrasonically with silver(I) oxide, generating a new metal-organic framework [Ag2(bpp)2(aze)·7H2O·CH3OH]n (1) that forms a 3D supramolecular structure through H-bonding interactions between solvent molecules and carboxylate O atoms with void spaces. Two kinds of solvent clusters, discrete cyclic (CH3OH)2(H2O)8 heterodecameric and acyclic water trimeric clusters occupy the channels in the structure. Furthermore, 1 exhibits strong photoluminescence maximized at 500 nm upon 350 nm excitation at room temperature, of which CIE chromaticity ordinate (x = 0.28, y = 0.44) is close to that of edge of green component.

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

PubMed

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

2014-03-28

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

Early Mars serpentinization-derived CH4 reservoirs, H2 induced warming and paleopressure evolution

NASA Astrophysics Data System (ADS)

Lasue, J.; Chassefiere, E.; Langlais, B.; Quesnel, Y.

2016-12-01

CH4 has been observed on Mars both by remote sensing and in situ during the past 15 years. Early Mars serpentinization is one possible abiotic mechanism that could not only produce methane, but also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. We recently estimated the maximum storage capacity of such clathrate layer to be about 2x1019 to 2x1020 moles of methane. Such reservoirs may be stable or unstable, depending on many factors that are poorly constrained: major and sudden geological events such as the Tharsis bulge formation, the Hellas impact or the martian polar wander, could have destabilized the clathrates early in the history of the planet and released large quantities of gas in the atmosphere. Here we estimate the associated amounts of serpentinization-derived CH4 stored in the cryosphere that have been released to the atmosphere at the end of the Noachian and the beginning of the Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. We propose that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several Myr or tens of Myr, having potentially contributed - by collision-induced heating effect of atmospheric H2 - to the formation of valley networks during the late Noachian and early Hesperian.

High-level ab initio predictions for the ionization energies and heats of formation of five-membered-ring molecules: thiophene, furan, pyrrole, 1,3-cyclopentadiene, and borole, C4H4X/C4H4X+ (X = S, O, NH, CH2, and BH).

PubMed

Lo, Po-Kam; Lau, Kai-Chung

2011-02-10

The ionization energies (IEs) and heats of formation (ΔH°(f0)/ΔH°(f298)) for thiophene (C(4)H(4)S), furan (C(4)H(4)O), pyrrole (C(4)H(4)NH), 1,3-cyclopentadiene (C(4)H(4)CH(2)), and borole (C(4)H(4)BH) have been calculated by the wave function-based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled-cluster level with single and double excitations plus a quasi-perturbative triple excitation [CCSD(T)]. Where appropriate, the zero-point vibrational energy correction (ZPVE), the core-valence electronic correction (CV), and the scalar relativistic effect (SR) are included in these calculations. The respective CCSD(T)/CBS predictions for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), being 8.888, 8.897, 8.222, and 8.582 eV, are in excellent agreement with the experimental values obtained from previous photoelectron and photoion measurements. The ΔH°(f0)/ΔH°(f298) values for the aforementioned molecules and their corresponding cations have also been predicted by the CCSD(T)/CBS method, and the results are compared with the available experimental data. The comparisons between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2) suggest that the CCSD(T)/CBS procedure is capable of predicting reliable IE values for five-membered-ring molecules with an uncertainty of ±13 meV. In view of the excellent agreements between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), the similar CCSD(T)/CBS IE and ΔH°(f0)/ΔH°(f298) predictions for C(4)H(4)BH, whose thermochemical data are not readily available due to its reactive nature, should constitute a reliable data set. The CCSD(T)/CBS IE(C(4)H(4)BH) value is 8.868 eV, and ΔH°(f0)/ΔH°(f298) values for C(4)H(4)BH and C(4)H(4)BH(+) are 269.5/258.6 and 1125.1/1114.6 kJ/mol, respectively. The highest occupied molecular orbitals

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

NASA Astrophysics Data System (ADS)

Narsimhulu, M.; Hussain, K. A.

2018-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

PubMed

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

Geographic Distribution of N2, CH4, CO2, and H2O Ices on Triton from Near-IR Spectroscopic Monitoring

NASA Astrophysics Data System (ADS)

Grundy, W. M.; Young, L. A.; Young, E. F.; Buie, M. W.; Spencer, J. R.

2004-11-01

We present new 0.8 to 2.4 μ m spectral observations of Neptune's satellite Triton, obtained at IRTF\\slash SpeX between 2001 and 2004 as part of an ongoing search for time-variable phenomena associated with Triton's seasonal volatile transport processes, and also perhaps with reported shorter-term "reddening" events. The ability to detect spectral changes on these time scales depends critically on accurate characterization of any cyclic variations resulting from Triton's 5.877 day rotation period. We will report on our observations of periodic variations of Triton's near-IR absorption bands of N2, CH4, and H2O ices, but not of CO2 ice, in this initial stage of our Triton monitoring program. The observed variations (or lack thereof) give an indication of how these four ice species are distributed in longitude. The most heterogeneously distributed ice is N2, which shows nearly twice as much absorption on Triton's Neptune-facing hemisphere as on the anti-Neptune hemisphere. Comparison with Voyager-era, visual wavelength imaging of Triton's surface suggest that the observed N2 ice is concentrated on low-latitude regions of Triton's polar cap, which are predominantly located on the Neptune-facing hemisphere. Non-volatile H2O ice seems to be slightly concentrated on Triton's leading hemisphere. Despite being highly diluted in N2 ice, the longitudinal distribution of Triton's CH4 ice differs from that of Triton's N2 ice, being slightly concentrated on Triton's trailing hemisphere. Triton's CO2 ice shows the least longitudinal variation, suggesting that it is either very uniformly distributed or that it is confined to high latitudes. This work was supported by NASA's Planetary Astronomy and Planetary Geology &\\ Geophysics programs, and by NSF's Planetary Astronomy program. \\hangindent=0.3truein Grundy, W.M., and L.A. Young (2004) Near infrared spectral monitoring of Triton with IRTF\\slash SpeX I: Establishing a baseline. Icarus (in press).

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

Effect of substituent groups (R= sbnd CH3, sbnd Br and sbnd CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes

NASA Astrophysics Data System (ADS)

Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2017-12-01

Complexes [Cr(3-CH3-pic)2(H2O)2]NO3·H2O (1), [Cr(5-Br-pic)2(H2O)2]NO3·H2O (2) and [Cr(5-CF3-pic)2(H2O)2]NO3·H2O (3) were synthesized (pic = pyridine-2-carboxylic acid) and characterized by X-ray crystal diffraction. Crystal structure indicates that two bidentate ligands occupy equatorial position and two H2O occupy axial positions in trans-configuration. (i) Decomposition of complexes 1, 2 and 3 in different medium (phosphate buffered saline (PBS), apo-ovotransferrin (apootf) and EDTA) indicates that decomposition rate constants of these complexes follow the sequence of 1 < 2 < 3. (ii) The redox potential of Cr(III)/Cr(II) by cyclic voltammetry follows the sequence of 1 (-1.20 V) > 3 (-1.29 V) > 2 (-1.31 V). (iii) In addition, ·OH-generation of the new synthesized complexes was determined by Fenton-like reaction in comparison with Cr(pic)3, and it may be related to the reduction potential of the complexes. (iv) Moreover, Hammett substituent constants σp (inductive) and σm (resonance) (R = 3-CH3, 5-Br, 5-CF3) were introduced to evaluate the impact of substituent groups on the bond length and decomposition kinetics. The substituent group on the ligand has great effect on the properties of the complexes.

Simultaneous in situ measurements and diurnal variations of NO, NO2, O3, jNO2, CH4, H2O, and CO2 in the 40- to 26-km region using an open path tunable diode laser spectrometer

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; May, Randy D.

1987-01-01

Simultaneous in situ measurements of temperature, pressure, and the NO, NO2, O3, jNO2, CH4, H2O, and CO2 concentrations were conducted in the 40- to 26-km region of the stratosphere using the JPL Balloon-borne Laser In Situ Sensor, a tunable diode laser absorption spectrometer. The NO, NO2, CH4, H2O, and CO2 concentration measurements generally show good agreement with previous observations, with a tendency for somewhat lower NO2 amounts. Measured O3 concentrations at 38 km agree well with comparable measurements from in situ UV photometers, but at 28 km they are lower by about 10 percent and agree more closely with the solar backscattered UV data. A decline was found in NO2 during the night over a 5-km altitude range, which implies either lower NO2 postsunset profiles, or an NO2 decay rate that is significantly higher than current model predictions that use N2O5 chemistry.

C-H and H-H Activation in Transition Metal Complexes and on Surfaces.

DTIC Science & Technology

1983-01-01

IEEIIIIIEEEEI EEEIIEIIIIIII EEIIIEIIIEIII IIIEEEIIEIIII La.𔃻 m41. 12.2 1.4o 12.0 1.25 111.4 11. MICROCOP RE SOO TESTCHAR NATIONA BUREA OfSANAD 16m ~4 OFFICE...ML4 plane, bringing a C-H bond in proximity to the metal. The compounds will minimize M. . C-H re- -27 - pulsion by bringing the H atom into an axial...h) C-H activation has been shown also with organolanthanides and organo- actinide compounds : Watson, P.L. J.Chem.Soc. Chem.Commun. 1983, 176-177

Interpreting activity in H(2)O-H(2)SO(4) binary nucleation.

PubMed

Bein, Keith J; Wexler, Anthony S

2007-09-28

Sulfuric acid-water nucleation is thought to be a key atmospheric mechanism for forming new condensation nuclei. In earlier literature, measurements of sulfuric acid activity were interpreted as the total (monomer plus hydrate) concentration above solution. Due to recent reinterpretations, most literature values for H(2)SO(4) activity are thought to represent the number density of monomers. Based on this reinterpretation, the current work uses the most recent models of H(2)O-H(2)SO(4) binary nucleation along with perturbation analyses to predict a decrease in critical cluster mole fraction, increase in critical cluster diameter, and orders of magnitude decrease in nucleation rate. Nucleation rate parameterizations available in the literature, however, give opposite trends. To resolve these discrepancies, nucleation rates were calculated for both interpretations of H(2)SO(4) activity and directly compared to the available parameterizations as well as the perturbation analysis. Results were in excellent agreement with older parameterizations that assumed H(2)SO(4) activity represents the total concentration and duplicated the predicted trends from the perturbation analysis, but differed by orders of magnitude from more recent parameterizations that assume H(2)SO(4) activity represents only the monomer. Comparison with experimental measurements available in the literature revealed that the calculations of the current work assuming a(a) represents the total concentration are most frequently in agreement with observations.

Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

NASA Astrophysics Data System (ADS)

Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

2017-09-01

Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

Investigation of H2S separation from H2S/CH4 mixtures using functionalized and non-functionalized vertically aligned carbon nanotube membranes

NASA Astrophysics Data System (ADS)

Gilani, Neda; Towfighi, Jafar; Rashidi, Alimorad; Mohammadi, Toraj; Omidkhah, Mohammad Reza; Sadeghian, Ahmad

2013-04-01

Separation of H2S from binary mixtures of H2S/CH4 using vertically aligned carbon nanotube membranes fabricated in anodic aluminum oxide (AAO) template was studied experimentally. Carbon nanotubes (CNTs) were grown in five AAO templates with different pore diameters using chemical vapor deposition, and CNT/AAO membranes with tubular carbon nanotube structure and open caps were selected for separation of H2S. For this, two tubular CNT/AAO membranes were fabricated with the CNT inner diameters of 23 and 8 nm. It was found that permeability and selectivity of the membrane with inner diameter of 23 nm for CNT were independent of upstream feed pressure and H2S feed concentration unlike that of CNT having an inner diameter of 8 nm. Selectivity of these membranes for separation of H2S was obtained in the ranges of 1.36-1.58 and 2.11-2.86, for CNTs with internal diameters of 23 and 8 nm, respectively. In order to enhance the separation of H2S from H2S/CH4 mixtures, dodecylamine was used to functionalize the CNT/AAO membrane with higher selectivity. The results showed that for amido-functionalized membrane, both upstream feed pressure and H2S partial pressure in the feed significantly increased H2S permeability, and selectivity for H2S being in the range of 3.0-5.57 respectively.

Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

PubMed

Sujith, K S; Ramachandran, C N

2016-02-07

The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

Selenium carboxylic acids betaine; 3,3‧,3″-selenotris(propanoic acid) betaine, Se(CH2CH2COOH)2(CH2CH2COO)

NASA Astrophysics Data System (ADS)

Doudin, Khalid; Törnroos, Karl W.

2017-06-01

Attempts to prepare [Se(CH2CH2COOH)3]+Cl- from Se(CH2CH2COOH)2 and H2Cdbnd CHCOOH in concentrated hydrochloric acid, for the corresponding sulfonium salt, led exclusively to the Se-betaine, Se(CH2CH2COOH)2(CH2CH2COO). The Se-betaine crystallises in the space group P2l/c with the cell dimensions at 223 K, a = 5.5717(1), b = 24.6358(4), c = 8.4361(1) Å, β = 104.762(1)°, V = 1119.74(3) Å3, Z = 4, Dcalc = 1.763 Mgm- 3, μ = 3.364 Mm-1. The structure refined to RI = 0.0223 for 2801 reflections with Fo > 4σ(Fo). In the crystalline state the molecule is intermolecularly linked to neighbouring molecules by a number of hydrogen bonds; a very strong carboxylic-carboxylate bond with an O⋯O distance of 2.4435(16) Å, a medium strong carboxylic-carboxylate bond with an O⋯O distance of 2.6431(16) Å and several weak O⋯H(CH2) with O⋯C distances between 3.2 and 3.3 Å. In the carboxylic group involved in the very strong hydrogen bond the O⋯H bond is antiperiplanar to the Cdbnd O bond while the Osbnd H bond is periplanar to the Cdbnd O bond in the second carboxylic group. Based upon the Csbnd O bond lengths and the elongation of the Osbnd H bond involved in the strong hydrogen bond one may describe the compound as strongly linked units of Se(CH2CH2COOH)(CH2CH2COO)2 rather than Se(CH2CH2COOH)2(CH2CH2COO). The selenium atom forms two strong intramolecular 1,5-Se⋯O contacts, with a carboxylate oxygen atom, 2.9385(12) Å, and with a carboxylic oxygen atom, 2.8979(11) Å. To allow for these contacts the two organic fragments have been forced into the periplanar conformation. The molecule is only slightly asymmetric with regard to the Csbnd Sesbnd C bond angles but is very asymmetric with regard to the torsion angles.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.; Song, Y.

2007-01-01

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (??1) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH4-H2O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 ??C, and pressures up to 37 MPa. The results show that the CH4 ??1 band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH4-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell. ?? 2007 Elsevier Ltd. All rights reserved.

Special hydrogen bonds observed in two monovalent metal carboxylate-phosphinates: {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2]·H2O}∞

NASA Astrophysics Data System (ADS)

Zhao, Cui-Cui; Zhang, Jian-Wei; Zhou, Zhong-Gao; Du, Zi-Yi

2013-02-01

The addition of strong base such as sodium hydroxide or potassium hydroxide to the aqueous solution of (2-carboxyethyl)(phenyl)phosphinic acid afforded two novel monovalent metal carboxylate-phosphinates, namely, {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ (1) and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2]·H2O}∞ (2). They represent the first examples of phosphinate containing short, symmetric or almost symmetric O⋯H⋯O hydrogen bonds.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Preparation, Characterization, and Structure of Two Layered Molybdenum(VI) Phosphates: KMo(H 2O)O 2PO 4 and NH 4Mo(H 2O)O 2PO 4

NASA Astrophysics Data System (ADS)

Millini, Roberto; Carati, Angela

1995-08-01

New layered Mo(VI) compounds, KMo(H 2O)O 2PO 4 (I) and NH 4Mo(H 2O)O 2PO 4 (II), were synthesized hydrothermally and their structures were determined from single-crystal X-ray analysis. Compounds (I) and (II) are isostructural and crystallize in the monoclinic P2 1/ n space group with a = 12.353(3), b = 8.623(2), c = 5.841(1) Å, β = 102.78(1)°, V = 606.8(2) Å 3, Z = 4, and R = 0.027 ( Rw = 0.030) for compound (I) and a = 12.435(3), b = 8.761(2), c = 6.015(1), β = 103.45(1)°, V = 637.3(2) Å 3, Z = 4, and R = 0.040 ( Rw = 0.041) for compound (II). The structure consists of layers built up of eight- and four-membered rings resulting from the alternation of corner-sharing [MoO 6] octahedra and [PO 4] tetrahedra. The layers stack along the (1¯01) direction by intercalating K and NH 4 ions.

New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

PubMed

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

Synthesis, crystal structure and thermal study of the hybrid nickel sulfate: C6N2H16[Ni(H2O)6(SO4)2].2H2O

NASA Astrophysics Data System (ADS)

Ngopoh, F. A. I.; Hamdi, N.; Chaouch, S.; Lachkar, M.; da Silva, I.; El Bali, B.

2018-03-01

A new inorganic-organic hybrid open framework nickel sulfate C6N2H16[Ni(H2O)6(SO4)2].2H2O has been synthesized by slow evaporation in aqueous solution using trans-1,4-diaminocyclohexane as structure-directing agent. It was characterized by single-crystal X-ray diffraction, infrared spectroscopy and analyzed by TGA-DSC. The compound crystallizes in the monoclinic space group P21/n, with the unit cell parameters of a = 6.2586 Å, b = 12.3009 Å, c = 13.2451 Å, β = 98,047°, Z = 4. Its crystal structure consists of isolated polyhedrons [Ni(H2O)6]2+ and [SO4]2- and free water which connects through hydrogen bonds. This association results in the porous framework where the protonated organic molecule trans-1,4-diaminocyclohexane is located as a counter ion. The IR spectra Shows the bands corresponding to the sulfate anion, water molecule and diprotonated trans-1-4-diaminocyclohexane. Thermal study indicates the loss of water molecules and the degradation of trans-1-4-diaminocyclohexane.

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

NASA Astrophysics Data System (ADS)

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

Release of N 2, CH 4, CO 2, and H 2O from surface ices on Enceladus

NASA Astrophysics Data System (ADS)

Hodyss, Robert; Goguen, Jay D.; Johnson, Paul V.; Campbell, Colin; Kanik, Isik

2008-09-01

We vapor deposit at 20 K a mixture of gases with the specific Enceladus plume composition measured in situ by the Cassini INMS [Waite, J.H., Combi, M.R., Ip, W.H., Cravens, T.E., McNutt, R.L., Kasprzak, W., Yelle, R., Luhmann, J., Niemann, H., Gell, D., Magee, B., Fletcher, G., Lunine, J., Tseng, W.L., 2006. Science 311, 1419-1422] to form a mixed molecular ice. As the sample is slowly warmed, we monitor the escaping gas quantity and composition with a mass spectrometer. Pioneering studies [Schmitt, B., Klinger, J., 1987. Different trapping mechanisms of gases by water ice and their relevance for comet nuclei. In: Rolfe, E.J., Battrick, B. (Eds.), Diversity and Similarity of Comets. SP-278. ESA, Noordwijk, The Netherlands, pp. 613-619; Bar-Nun, A., Kleinfeld, I., Kochavi, E., 1988. Phys. Rev. B 38, 7749-7754; Bar-Nun, A., Kleinfeld, I., 1989. Icarus 80, 243-253] have shown that significant quantities of volatile gases can be trapped in a water ice matrix well above the temperature at which the pure volatile ice would sublime. For our Enceladus ice mixture, a composition of escaping gases similar to that detected by Cassini in the Enceladus plume can be generated by the sublimation of the H 2O:CO 2:CH 4:N 2 mixture at temperatures between 135 and 155 K, comparable to the high temperatures inferred from the CIRS measurements [Spencer, J.R., Pearl, J.C., Segura, M., Flasar, F.M., Mamoutkine, A., Romani, P., Buratti, B.J., Hendrix, A.R., Spilker, L.J., Lopes, R.M.C., 2006. Science 311, 1401-1405] of the Enceladus "tiger stripes." This suggests that the gas escape phenomena that we measure in our experiments are an important process contributing to the gases emitted from Enceladus. A similar experiment for ice deposited at 70 K shows that both the processes of volatile trapping and release are temperature dependent over the temperature range relevant to Enceladus.

Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

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

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

2015-03-15

Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

Chemical dynamics simulations of the monohydrated OH-(H2O) + CH3I reaction. Atomic-level mechanisms and comparison with experiment

NASA Astrophysics Data System (ADS)

Xie, Jing; Otto, Rico; Wester, Roland; Hase, William L.

2015-06-01

Direct dynamics simulations, with B97-1/ECP/d theory, were performed to study the role of microsolvation for the OH-(H2O) + CH3I reaction. The SN2 reaction dominates at all reactant collision energies, but at higher collision energies proton transfer to form CH2I-, and to a lesser extent CH2I- (H2O), becomes important. The SN2 reaction occurs by direct rebound and stripping mechanisms, and 28 different indirect atomistic mechanisms, with the latter dominating. Important components of the indirect mechanisms are the roundabout and formation of SN2 and proton transfer pre-reaction complexes and intermediates, including [CH3--I--OH]-. In contrast, for the unsolvated OH- + CH3I SN2 reaction, there are only seven indirect atomistic mechanisms and the direct mechanisms dominate. Overall, the simulation results for the OH-(H2O) + CH3IߙSN2 reaction are in good agreement with experiment with respect to reaction rate constant, product branching ratio, etc. Differences between simulation and experiment are present for the SN2 velocity scattering angle at high collision energies and the proton transfer probability at low collision energies. Equilibrium solvation by the H2O molecule is unimportant. The SN2 reaction is dominated by events in which H2O leaves the reactive system as CH3OH is formed or before CH3OH formation. Formation of solvated products is unimportant and participation of the (H2O)CH3OH---I- post-reaction complex for the SN2 reaction is negligible.

Effects on H(-) production in a multicusp ion source by mixture of H2 with H2O, NH3, CH4, N2H4, and SF6

NASA Technical Reports Server (NTRS)

Orient, O. J.; Chutjian, A.; Leung, K. N.

1987-01-01

Effects of H(-) production in a multicusp ion source are measured by separately mixing with hydrogen small amounts (0.33-10 percent) of water, ammonia, methane, and hydrazine these are molecules which produce large amounts of H(-) via dissociative attachment (DA) resonances at higher electron energies. The mixing was done in a separate reservoir, with careful measurement of individual pressures. Experimental enhancements of 1.4 and less were observed, whereas calculated enhancements, using accurate DA cross sections for ground-state H2, should have produced factors of 1.5, 3.0, 1.3, and 2.4 enhancements for water, ammonia methane, and hydrazine, respectively, at a mean electron energy of 1.0 eV in the extraction region. The difference is accounted for by including, in the enhancement calculation, vibrationally and rotationally excited H2 molecules, with v-double prime = 5-11, and J-double prime = 0-5, and the large DA cross sections for the excited H2 (v-double prime, J-double prime). The relative populations of H2 (v-double prime, J-double prime) thus obtained are found to be substantially smaller than those predicted by theoretical calculations. The effect on H(-) current was also studied by mixing small amounts of SF6 with H2. A 1.5 percent mixture was found to reduce the H(-) output by one half.

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 2. The systems H(+)-HSO4(-)-SO4(2-)-H2O from 0 to 3 mol kg(-1) as a function of temperature and H(+)-NH4(+)-HSO4(-)-SO4)2-)-H2O from 0 to 6 mol kg(-1) at 25 °C using a Pitzer ion interaction model, and NH4HSO4-H2O and (NH4)3H(SO4)2-H2O over the entire concentration range.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

A Pitzer ion interaction model has been applied to the systems H(2)SO(4)-H(2)O (0-3 mol kg(-1), 0-55 °C) and H(2)SO(4)-(NH(4))(2)SO(4)-H(2)O (0-6 mol kg(-1), 25 °C) for the calculation of apparent molar volume and density. The dissociation reaction HSO(4)(-)((aq)) ↔ H(+)((aq)) + SO(4)(2-)((aq)) is treated explicitly. Apparent molar volumes of the SO(4)(2-) ion at infinite dilution were obtained from part 1 of this work, (1) and the value for the bisulfate ion was determined in this study from 0 to 55 °C. In dilute solutions of both systems, the change in the degree of dissociation of the HSO(4)(-) ion with concentration results in much larger variations of the apparent molar volumes of the solutes than for conventional strong (fully dissociated) electrolytes. Densities and apparent molar volumes are tabulated. Apparent molar volumes calculated using the model are combined with other data for the solutes NH(4)HSO(4) and (NH(4))(3)H(SO(4))(2) at 25 °C to obtain apparent molar volumes and densities over the entire concentration range (including solutions supersaturated with respect to the salts).

Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen.

PubMed