Detection of interstellar N2O: A new molecule containing an N-O bond

NASA Astrophysics Data System (ADS)

Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

1994-12-01

A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is Ntot approx. 1015/sq. cm, which corresponds to a fractional abundance of approx. 10-9, relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

An improved method of measuring tropospheric NO2, NO3, HO2, and RO2 by Matrix Isolation and Electronic Spin Resonance (MIESR)

NASA Technical Reports Server (NTRS)

1994-01-01

The MIESR method consists of two steps (1) collection of the radicals present in the ambient air at 77K in a polycrystalline D2O matrix and (2) identification and quantification of the different radicals in the laboratory by Electron Spin Resonance spectroscopy. In step (1), the sampling efficiency for sampling NO2 and RO2 was determined to be greater than or equal to 95 percent, with a measured accuracy of plus or minus 5 percent. In step (2), after collection, the samples are maintained at 77 K and spectra are recorded in the laboratory using a standard 9.5 GHz ESR system (Varian E-line). About 50 individual scans of each spectrum are recorded and digitally averaged in order to improve the signal-to-noise ratio. The ESR-spectra are analyzed with a recently developed numerical procedure which was demonstrated to allow speciation of NO2, NO3, HO2, CH3C(O)O2, and the sum of the alkylperoxy radicals. The detection limit is 5ppt for HO2, RO2, and NO2 and 3ppt for NO3 due to its narrower ESR-linewidth.

The reactions of SO3 with HO2 radical and H2O...HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4.

PubMed

Gonzalez, Javier; Torrent-Sucarrat, Miquel; Anglada, Josep M

2010-03-07

The influence of a single water molecule on the gas-phase reactivity of the HO(2) radical has been investigated by studying the reactions of SO(3) with the HO(2) radical and with the H(2)O...HO(2) radical complex. The naked reaction leads to the formation of the HSO(5) radical, with a computed binding energy of 13.81 kcal mol(-1). The reaction with the H(2)O...HO(2) radical complex can give two different products, namely (a) HSO(5) + H(2)O, which has a binding energy that is computed to be 4.76 kcal mol(-1) more stable than the SO(3) + H(2)O...HO(2) reactants (Delta(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol(-1) below the energy of the reactants (Delta(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H(2)SO(4) may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO(2), HSO(5), the HSO(5)...H(2)O hydrogen bonded complex, H(2)SO(4), and two H(2)SO(4)...H(2)O complexes, in order to help with the possible experimental identification of some of these species.

Near IR Photolysis of HO2NO2: Supplemental Material

NASA Technical Reports Server (NTRS)

2002-01-01

MkIV measurements of the volume mixing ratio (VMR) of HO2NO2 at 35 deg N, sunset on Sept. 25, 1993 are given. Measurements of HO2NO2 made between approx. 65 and 70 deg N, sunrise on May 8, 1997 are listed. The uncertainties given are 1 sigma estimates of the measurement precision. Uncertainty in the HO2NO2 line strengths is estimated to be 20%; this is the dominant contribution to the systematic error of the HO2NO2 measurement. Model inputs for the simulations are given. The albedos were obtained from Total Ozone Mapping Spectrometer reflectively data (raw data at ftp://jwocky.gsfc.nasa.gov) for the time and place of observation. Profiles of sulfate aerosol surface area ("Surf. Area") were obtained from monthly, zonal mean profiles measured by SAGE II [Thomason et al., 1997 updated via private communication]. The profile of Be(y) is based on the Wamsley et al. relation with N2O, using MkIV measurements of N20O. All other model inputs given are based on direct MkIV measurements. Finally, we note the latitude of the MkIV tangent point varied considerably during sunrise on May 8, 1997. The simulations shown here were obtained using different latitudes for each altitude.

Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses for ∼1.2 μm laser applications

NASA Astrophysics Data System (ADS)

Wang, Shunbin; Li, Chengzhi; Yao, Chuanfei; Jia, Shijie; Jia, Zhixu; Qin, Guanshi; Qin, Weiping

2017-02-01

Intense ∼1.2 μm fluorescence is observed in Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses under 915 nm laser diode excitation. The 1.2 μm emission can be ascribed to the transition 5I6→5I8 of Ho3+. With the introducing of BaF2, the content of OH in the glasses drops markedly, and the 1.2 μm emission intensity increases gradually as increasing the concentration percentage of BaF2. Furthermore, microstructured fibers based on the TeO2-BaF2-Y2O3 glasses are fabricated by using a rod-in-tube method, and a relative positive gain of ∼9.42 dB at 1175.3 nm is obtained in a 5 cm long fiber.

Theoretical Study on the Dynamics of the Reaction of HNO((1)A') with HO2((2)A″).

PubMed

Mousavipour, S Hosein; Asemani, S Somayeh

2015-06-04

We used stochastic one-dimensional chemical master equation (CME) simulation to gain insight into the dynamics of the reaction of HNO((1)A') with HO2((2)A″). The reaction takes place over a multiwell, multichannel potential energy surface that is based on the computations at the CBS-QB3 level of theory. The calculated multipath potential energy surface consists of three potential wells and three van der Waals complexes. In solving the master equation, the Lennard-Jones potential is used to model the collision between the collider gases. The fractional population of different intermediates and products in the early stages of the reaction is examined to determine the role of the energized intermediates and van der Waals complexes on the kinetics of the title reaction. The major products of the title reaction at lower temperatures are OH, HNO2, HNOH, and O2(X(3)Σg(-)). The temperature- and pressure-dependence of the reaction over a wide range of temperature (300-3000 K) and pressure (0.1-2000 Torr) are studied. No sign of pressure dependence was being observed for the title reaction over the stated range of pressure. The calculated rate constants from the CME simulation are compared with those obtained from the RRKM-SSA method that is based on strong collision assumption. Our results indicate that the strong collision assumption increases the calculated rate constant for the formation of the main products (HNO2 + OH) by a factor of 2 at 300 K and 1 atm pressure, compared to the results of CME simulation, although the results are in good agreement at higher temperatures.

Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

NASA Technical Reports Server (NTRS)

Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

1988-01-01

Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

The HO2 + (H2O)n + O3 reaction: an overview and recent developments*

NASA Astrophysics Data System (ADS)

Viegas, Luís P.; Varandas, António J. C.

2016-03-01

The present work is concerned with the reaction of the hydroperoxyl radical with ozone, which is key in the atmosphere. We first give a brief overview which emphasizes theoretical work developed at the authors' Group, considering not only the naked reaction (n = 0) but also the reaction with one water molecule added to the reactants (n = 1). Aiming at a broad and contextual understanding of the role of water, we have also very recently published the results of the investigation considering the addition of water dimers (n = 2) and trimers (n = 3) to the reactants. Such results are also succinctly addressed before we present our latest and unpublished research endeavors. These consist of two items: the first one addresses a new mechanistic pathway for hydrogen-abstraction in n = 2-4 cases, in which we observe a Grotthuss-like hydrogen shuttling mechanism that interconverts covalent and hydrogen bonds (water molecules are no longer spectators); the second addresses our exploratory calculations of the HO2 + O3 reaction inside a (H2O)20 water cage, where we strive to give a detailed insight of the molecular processes behind the uptake of gas-phase molecules by a water droplet. Supplementary material in the form of one zip file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2016-60733-5Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

The diurnal variation of hydrogen, nitrogen, and chlorine radicals: Implications for the heterogeneous production of HNO2

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.

1994-01-01

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower statosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heteogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of (OH) and (HO2) coincides with the rise of (NO) from photolysis of NO2, suggesting a new source of HO(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allow for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).

Establishing the Dependence of [HO2]/[OH] on Temperature, Halogen Loading, O3, and NO(x) Based on in Situ Measurements from the NASA ER-2

NASA Technical Reports Server (NTRS)

Lanzendorf, E. J.; Hanisco, T. F.; Wennberg, P. O.; Cohen, R. C.; Stimpfle, R. M.; Anderson, J. G.; Gao, R. S.; Margitan, J. J.; Bui, T. P.

2001-01-01

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Photochemical removal of NO(2) by using 172-nm Xe(2) excimer lamp in N(2) or air at atmospheric pressure.

PubMed

Tsuji, Masaharu; Kawahara, Masashi; Noda, Kenji; Senda, Makoto; Sako, Hiroshi; Kamo, Naohiro; Kawahara, Takashi; Kamarudin, Khairul Sozana Nor

2009-03-15

Photochemical removal of NO(2) in N(2) or air (5-20% O(2)) mixtures was studied by using 172-nm Xe(2) excimer lamps to develop a new simple photochemical aftertreatment technique of NO(2) in air at atmospheric pressure without using any catalysts. When a high power lamp (300 mW/cm(2)) was used, the conversion of NO(2) (200-1000 ppm) to N(2) and O(2) in N(2) was >93% after 1 min irradiation, whereas that to N(2)O(5), HNO(3), N(2), and O(2) in air (10% O(2)) was 100% after 5s irradiation in a batch system. In a flow system, about 92% of NO(2) (200 ppm) in N(2) was converted to N(2) and O(2), whereas NO(2) (200-400 ppm) in air (20% O(2)) could be completely converted to N(2)O(5), HNO(3), N(2), and O(2) at a flow rate of 1l/min. It was found that NO could also be decomposed to N(2) and O(2) under 172-nm irradiation, though the removal rate is slower than that of NO(2) by a factor of 3.8. A simple model analysis assuming a consecutive reaction NO(2)-->NO-->N+O indicated that 86% of NO(2) is decomposed directly into N+O(2) and the rest is dissociated into NO+O under 172-nm irradiation. These results led us to conclude that the present technique is a new promising catalyst-free photochemical aftertreatment method of NO(2) in N(2) and air in a flow system.

Effect of concentration variation on 2.0 µm emission of Ho3+-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 oxyfluorosilicate glasses

NASA Astrophysics Data System (ADS)

Gelija, Devarajulu; Borelli, Deva Prasad Raju

2018-02-01

The concentration variation of Ho3+ ion-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 glasses has been prepared by conventional melt quenching method. The thermal stability of 1 mol % of Ho3+-doped oxyfluorosilicate glass has been calculated using the differential thermal analysis (DTA) spectra. The phenomenological Judd-Ofelt intensity parameters Ωλ ( λ = 2, 4 and 6) were calculated for all concentrations of Ho3+ ions. The luminescence spectra in visible region of Ho3+ ion-doped glasses were recorded under the excitation wavelength of 452 nm. The spectra consists of several intense emission bands (5F4, 5S2) → 5I8 (547 nm), 5F3 → 5I8 (647 nm), 5F5 → 5I7 (660 nm) and (5F4, 5S2) → 5I7 (750 nm) in the range 500-780 nm. The fluorescence emission at ˜2.0 µm (5I7 → 5I8) was observed under the excitation of 488 nm Ar-ion laser. The stimulated emission cross section for 5I7 → 5I8 transition (˜2.0 µm) varies from 8.46 to 9.52 × 10-21 cm2, as calculated by the Fuchtbauer-Ladenburg (FL) theory. However, Mc-Cumber theory was used to calculate emission cross section values about 4.24-5.75 × 10-21 cm2 for the 5I7 → 5I8 transition in all concentrations of Ho3+-doped oxyfluorosilicate glasses. Therefore, these results reveal that the 0.5 mol % of Ho3+-doped oxyfluorosilicate glasses, exhibiting higher emission cross section, has potentially been used for laser applications at ˜ 2.0 µm.

Uptake of methanol on mixed HNO3/H2O clusters: An absolute pickup cross section

NASA Astrophysics Data System (ADS)

Pysanenko, A.; Lengyel, J.; Fárník, M.

2018-04-01

The uptake of atmospheric oxidized organics on acid clusters is relevant for atmospheric new particle formation. We investigate the pickup of methanol (CH3OH) on mixed nitric acid-water clusters (HNO3)M(H2O)N by a combination of mass spectrometry and cluster velocity measurements in a molecular beam. The mass spectra of the mixed clusters exhibit (HNO3)m(H2O)nH+ series with m = 0-3 and n = 0-12. In addition, CH3OH.(HNO3)m(H2O)nH+ series with very similar patterns appear in the spectra after the methanol pickup. The velocity measurements prove that the undoped (HNO3)m(H2O)nH+ mass peaks in the pickup spectra originate from the neutral (HNO3)M(H2O)N clusters which have not picked up any CH3OH molecule, i.e., methanol has not evaporated upon the ionization. Thus the fraction of the doped clusters can be determined and the mean pickup cross section can be estimated, yielding σs ¯ ≈ 20 Å2. This is compared to the lower estimate of the mean geometrical cross section σg ¯ ≈ 60 Å2 obtained from the theoretical cluster geometries. Thus the "size" of the cluster corresponding to the methanol pickup is at least 3-times smaller than its geometrical size. We have introduced a method which can yield the absolute pickup cross sections relevant to the generation and growth of atmospheric aerosols, as illustrated in the example of methanol and nitric acid clusters.

Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

NASA Technical Reports Server (NTRS)

Wendt, J.; Fabian, Peter; Flentje, G.; Kourtidis, K.

1994-01-01

A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Model simulation of NO3, N2O5 and ClNO2 at a rural site in Beijing during CAREBeijing-2006

NASA Astrophysics Data System (ADS)

Wang, Haichao; Lu, Keding; Tan, Zhaofeng; Sun, Kang; Li, Xin; Hu, Min; Shao, Min; Zeng, Limin; Zhu, Tong; Zhang, Yuanhang

2017-11-01

A chemical box model was used to study nitrate radical (NO3), dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) in a rural site during the Campaign of Air Quality Research in Beijing 2006 (CAREBeijing-2006). The model was based on regional atmospheric chemistry mechanism version 2 (RACM2) with the heterogeneous uptake of N2O5 and the simplified chloride radical (Cl) chemistry mechanism. A high production rate of NO3 with a mean value of 0.8 ppbv/h and low mixing ratios of NO3 and N2O5 (peak values of 17 pptv and 480 pptv, respectively) existed in this site. Budget analysis showed that NO emission suppressed the NO3 chemistry at the surface layer, the reaction of NO3 with VOCs made a similar contribution to NO3 loss as N2O5 heterogeneous uptake. The NO3 chemistry was predominantly controlled by isoprene, and NO3 oxidation produced organic nitrate with a mean value of 0.06 ppbv/h during nighttime. The organic nitrate production initiated by NO3 was equal to that initiated by OH, implying the importance of nighttime chemistry for secondary organic aerosol (SOA) formation. We confirmed that the N2O5 heterogeneous reaction accounted for nighttime particle NO3- enhancement, with a large day to day variability, and made less of a contribution to NOx loss compared to that of OH reacting with NO2. Additionally, abundant ClNO2, up to 5.0 ppbv, was formed by N2O5 heterogeneous uptake. ClNO2 was sustained at a high level until noon in spite of the gradually increasing photolysis of ClNO2 after sunrise. Chlorine activation caused by N2O5 heterogeneous uptake increased primary ROx formation by 5% and accounted for 8% of the net ozone production enhancement in the morning.

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.

Observations of different core water cluster ions Y-(H2O)n (Y = O2, HOx, NOx, COx) and magic number in atmospheric pressure negative corona discharge mass spectrometry.

PubMed

Sekimoto, Kanako; Takayama, Mitsuo

2011-01-01

Reliable mass spectrometry data from large water clusters Y(-)(H(2)O)(n) with various negative core ions Y(-) such as O(2)(-), HO(-), HO(2)(-), NO(2)(-), NO(3)(-), NO(3)(-)(HNO(3))(2), CO(3)(-) and HCO(4)(-) have been obtained using atmospheric pressure negative corona discharge mass spectrometry. All the core Y(-) ions observed were ionic species that play a central role in tropospheric ion chemistry. These mass spectra exhibited discontinuities in ion peak intensity at certain size clusters Y(-)(H(2)O)(m) indicating specific thermochemical stability. Thus, Y(-)(H(2)O)(m) may correspond to the magic number or first hydrated shell in the cluster series Y(-)(H(2)O)(n). The high intensity discontinuity at HO(-)(H(2)O)(3) observed was the first mass spectrometric evidence for the specific stability of HO(-)(H(2)O)(3) as the first hydrated shell which Eigen postulated in 1964. The negative ion water clusters Y(-)(H(2)O)(n) observed in the mass spectra are most likely to be formed via core ion formation in the ambient discharge area (760 torr) and the growth of water clusters by adiabatic expansion in the vacuum region of the mass spectrometers (≈1 torr). The detailed mechanism of the formation of the different core water cluster ions Y(-)(H(2)O)(n) is described. Copyright © 2010 John Wiley & Sons, Ltd.

Quenching of I(2P1/2) by NO2, N2O4, and N2O.

PubMed

Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

2007-10-11

Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.

The temperature dependence of the reactions of HO2 with NO and NO2

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Heicklen, J.

1977-01-01

Mixtures of N2O, H2, O2 and trace amounts of NO and NO2 were photolyzed at 213.9 nm at 245-328 K and about 1 atm total pressure (mostly H2). HO2 radicals are produced from the photolysis, and their reactions are reported.

The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

NASA Technical Reports Server (NTRS)

Cantrell, C. A.; Davidson, J. A.; Mcdaniel, A. H.; Shetter, R. E.; Calvert, J. G.

1988-01-01

Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

Pulsed laser photolysis study of the reaction between O(3P) and HO2

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.; Nicovich, J. M.

1983-01-01

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO.

PubMed

Raghunath, P; Lee, Yuan-Pern; Lin, M C

2017-05-25

The kinetics and mechanisms for the reaction of the Criegee intermediate CH 2 OO with HNO 3 and the unimolecular decomposition of its reaction product CH 2 (O)NO 3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO 3 CH 2 OOH* with internal energy ∼44 kcal mol -1 . A fragmentation of this excited intermediate produces CH 2 (O)NO 3 + OH with its transition state located 5.0 kcal mol -1 below that of the reactants. Further decomposition of CH 2 (O)NO 3 produces HCO + HNO 3 , forming a catalytic cycle for destruction of CH 2 OO by HNO 3 . The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N 2 ) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH 2 OO + HNO 3 at 295 K, 5.1 × 10 -10 cm 3 molecule -1 s -1 , agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10 -10 cm 3 molecule -1 s -1 . The predicted branching ratios at 295 K are 0.21 for the formation of NO 3 CH 2 OOH and 0.79 for CH 2 (O)NO 3 + OH at a pressure of 40 Torr (N 2 ), and 0.79 for the formation of NO 3 CH 2 OOH and 0.21 for CH 2 (O)NO 3 + OH at 760 Torr (N 2 ). This new catalytic conversion of CH 2 OO to HCO + OH by HNO 3 might have significant impact on atmospheric chemistry.

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

PubMed

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

2012-02-20

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

Polymorph (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho-Lu, Y) and REF{sub 3} nanocrystals: Hydrothermal synthesis, characterization and luminescence

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

Jia, Li-Ping; Zhang, Qiang; Yan, Bing, E-mail: byan@tongji.edu.cn

Graphical abstract: A hydrothermal system is developed to prepare one new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O and known rare earth fluorides involving REF{sub 3} nanocrystals under mild condition. Highlights: ► A new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O has been synthesized. ► The RE{sup 3+} radius decides the shape evolution and phase control for REF{sub 3} NCs. ► The RE{sup 3+} radius has influence on the microstructure and morphology of REF{sub 3} NCs. -- Abstract: In this paper, a solvents-thermal system is developed to prepare one new polymorph of (C{sub 2}N{submore » 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O and rare earth fluorides REF{sub 3} nanocrystals under mild condition. It is found that the ionic radius of RE{sup 3+} is the key factor responsible for the shape evolution and phase control for rare earth fluorides nanocrystals at selected temperatures, which has an influence on the microstructure and morphology of the products to some extent. With the increase of the atomic number, the shape of fluoride changes from hexagonal REF{sub 3} phase (RE = La, Sm) to orthorhombic REF{sub 3} phase (RE = Eu-Dy), and finally to diamond structure (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho, Er, Tm, Yb, Lu, Y). In addition, the characteristic energy level transition {sup 5}D{sub 0}–{sup 7}F{sub 1} of Eu{sup 3+} splits into 585 and 591 nm emission peaks, and the dominant peak is the orange emission at 591 nm.« less

Balloon Profiles of Stratospheric NO(sub 2) and HNO(sub 3) for Testing the Heterogeneous Hydrolysis of N(sub 2)O(sub 5) on Sulfate Aerosols

NASA Technical Reports Server (NTRS)

Webster, C. R.; May, R. D.; Allen, M.; Jaegle, L.; McCormick, M. P.

1993-01-01

Simultaneous in situ measurements of stratospheric NO(sub 2), HNO(sub 3), HCI, and CH(sub 4) from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS)tunable diode laser spectrometer.

Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

PubMed Central

Paschalidis, Damianos G.; Harrison, William T. A.

2016-01-01

The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

Method and apparatus for synthesizing HMX and N/sub 2/O/sub 5/. [Patent application; cyclotetramethylenetetraamine

DOEpatents

McGuire, R.R.; Coon, C.L.; Harrar, J.E.; Pearson, R.K.

1982-07-20

A method and apparatus for electrochemically synthesizing N/sub 2/O/sub 5/ includes oxidizing a solution of N/sub 2/O/sub 4//HNO/sub 3/ at an anode, while maintaining a controlled potential between the N/sub 2/O/sub 4//HNO/sub 3/ solution and the anode. A potential of about 1.35 to 2.0V vs. SCE is preferred, while a potential of about 1.80V vs. SCE is most preferred. Thereafter, the N/sub 2/O/sub 5/ is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

The chemistry of bromine in the stratosphere: Influence of a new rate constant for the reaction BrO + HO2

NASA Technical Reports Server (NTRS)

Pirre, Michel; Marceau, Francois J.; Lebras, Georges; Maguin, Francoise; Poulet, Gille; Ramaroson, Radiela

1994-01-01

The impact of new laboratory data for the reaction BrO + HO2 yields HOBr + O2 in the depletion of global stratospheric ozone has been estimated using a one-dimensional photochemical model taking into account the heterogeneous reaction on sulphate aerosols which converts N2O5 into HNO3. Assuring an aerosol loading 2 times as large as the 'background' and a reaction probability of 0.1 for the above heterogeneous reaction, the 6 fold increase in the measured rate constant for the reaction of BrO with HO2 increases the computed depletion of global ozone produced by 20 ppt of total bromine from 2.01 percent to 2.36 percent. The use of the higher rate constant increases the HOBr mixing ratio and makes the bromine partitioning and the ozone depletion very sensitive to the branching ratio of the potential channel forming HBr in the BrO + HO2 reaction.

Formation of nitro-PAHs from the heterogeneous reaction of ambient particle-bound PAHs with N2O5/NO3/NO2

PubMed Central

Zimmermann, Kathryn; Jariyasopit, Narumol; Massey Simonich, Staci L.; Tao, Shu; Atkinson, Roger; Arey, Janet

2014-01-01

Reactions of ambient particles collected from four sites within the Los Angeles, CA air basin and Beijing, China with a mixture of N2O5, NO2, and NO3 radicals were studied in an environmental chamber at ambient pressure and temperature. Exposures in the chamber system resulted in the degradation of particle-bound PAHs and formation of molecular weight (mw) 247 nitropyrenes (NPYs) and nitrofluoranthenes (NFLs), mw 273 nitrotriphenylenes (NTPs), nitrobenz[a]anthracenes (NBaAs), and nitrochrysene (NCHR), and mw 297 nitrobenzo[a]pyrene (NBaP). The distinct isomer distributions resulting from exposure of filter-adsorbed deuterated fluoranthene to N2O5/NO3/NO2 and that collected from the chamber gas-phase suggest that formation of NFLs in ambient particles did not occur by NO3 radical-initiated reaction, but from reaction of N2O5, presumably subsequent to its surface adsorption. Accordingly, isomers known to result from gas-phase radical-initiated reactions of parent PAHs, such as 2-NFL and 2- and 4-NPY, were not enhanced from the exposure of ambient particulate matter to N2O5/NO3/NO2. The reactivity of ambient particles toward nitration by N2O5/NO3/NO2, defined by relative 1-NPY formation, varied significantly, with the relative amounts of freshly emitted particles versus aged particles (particles that had undergone atmospheric chemical processing) affecting the reactivity of particle-bound PAHs toward heterogeneous nitration. Analyses of unexposed ambient samples suggested that, in nighttime samples where NO3 radical-initiated chemistry had occurred, heterogeneous formation of 1-NPY on ambient particles may have contributed to the ambient 1-NPY concentrations at downwind receptor sites. These results, together with observations that 2-NFL is consistently the dominant particle-bound nitro-PAH measured in ambient atmospheres, suggest that for PAHs that exist in both the gas- and particle-phase, the heterogeneous formation of particle-bound nitro-PAHs is a minor formation

Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

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

Kazmierczak, Karolina; Hoeppe, Henning A., E-mail: henning@ak-hoeppe.d

2011-05-15

The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrationalmore » and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.« less

Near-infrared kinetic spectroscopy of the HO2 and C2H5O2 self-reactions and cross reactions.

PubMed

Noell, A C; Alconcel, L S; Robichaud, D J; Okumura, M; Sander, S P

2010-07-08

The self-reactions and cross reactions of the peroxy radicals C2H5O2 and HO2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO2, and UV absorption monitored C2H5O2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221-296 K. The Arrhenius expression determined for the cross reaction, k2(T) = (6.01(-1.47)(+1.95)) x 10(-13) exp((638 +/- 73)/T) cm3 molecules(-1) s(-1) is in agreement with other work from the literature. The measurements of the HO2 self-reaction agreed with previous work from this lab and were not further refined. The C2H5O2 self-reaction is complicated by secondary production of HO2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO2. The Arrhenius expression for the self-reaction rate constant is k3(T) = (1.29(-0.27)(+0.34)) x 10(-13)exp((-23 +/- 61)/T) cm3 molecules(-1) s(-1), and the branching fraction value is alpha = 0.28 +/- 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO2 self-reactions are required.

Temperature Dependence of the O + HO2 Rate Coefficient

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

A new cavity ring-down instrument for airborne monitoring of N2O5, NO3, NO2 and O3 in the upper troposphere lower stratosphere

NASA Astrophysics Data System (ADS)

Ruth, Albert A.; Brown, Steven S.; Dinesan, Hemanth; Dubé, William P.; Goulette, Marc; Hübler, Gerhard; Orphal, Johannes; Zahn, Andreas

2016-04-01

The chemistry of NO3 and N2O5 is important to the regulation of both tropospheric and stratospheric ozone. In situ detection of NO3 and N2O5 in the upper troposphere lower stratosphere (UTLS) represents a new scientific direction as the only previous measurements of these species in this region of the atmosphere has been via remote sensing techniques. Because both the sources and the sinks for NO3 and N2O5 are potentially stratified spatially, their mixing ratios, and their influence on nitrogen oxide and ozone transport and loss at night can show large variability as a function of altitude. Aircraft-based measurements of heterogeneous N2O5 uptake in the lower troposphere have uncovered a surprising degree of variability in the uptake coefficient [1], but there are no corresponding high altitude measurements.The UTLS is routinely sampled by the IAGOS-CARIBIC program (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com), a European infrastructural program with the aim of studying the chemistry and transport across this part of the atmosphere. An airfreight container with 15 different automated instruments from 8 European research partners is utilized on board a commercial Lufthansa airbus 340-600 to monitor ~ 100 atmospheric species (trace gases and aerosol parameters) in the UTLS. The instrumentation in the CARIBIC container is now to be supplemented by a new cavity ring-down device for monitoring nitrogen oxides, jointly developed by researchers from Cork (Ireland), Boulder (USA) and Karlsruhe (Germany). The compact and light-weight instrument is designed to monitor not only NO3 and N2O5, but also NO2 and O3. The detection is based on 4 high-finesse optical cavities (cavity length ~ 44 cm). Two cavities are operated at 662 nm (maximum absorption of NO3), the other two at 405 nm (maximum absorption of NO2). The inlet to one of the (662)-cavities is heated in order to thermally decompose N2O5

Tris(5,6-dimethyl-1H-benzimidazole-κN(3))(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))nickel(II).

PubMed

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-06-01

The title mononuclear complex, [Ni(C(7)H(3)NO(4))(C(9)H(10)N(2))(3)], shows a central Ni(II) atom which is coordinated by two carboxyl-ate O atoms and the N atom from a pyridine-2,6-dicarboxyl-ate ligand and by three N atoms from different 5,6-dimethyl-1H--benzimidazole ligands in a distorted octa-hedral geometry. The crystal structure shows intermolecular N-H⋯O hydrogen bonds.

On the role of the termolecular reactions 2O2 + H2 → 2HO2 and 2O2 + H2 → H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

PubMed

Monge-Palacios, M; Rafatijo, Homayoon

2017-01-18

We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2 → H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2 → H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 2 → 2HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2 → H + HO 2 + O 2 and two for 2O 2 + H 2 → 2HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 2 → 2HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2 → H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2 → H + HO 2 only at sufficiently high pressures.

Broad band and enhanced photocatalytic behaviour of Ho3+-doped Bi2O3 micro-rods

NASA Astrophysics Data System (ADS)

Prasad, Neena; Karthikeyan, Balasubramanian

2018-06-01

Band-gap-tuned Bi2O3 micro-rods were synthesized using simple co-precipitation method by doping 5 wt% Ho3+ to mitigate the concentration of toxic dye from the polluted water using it as a photocatalyst. Structure and morphology of the prepared samples were identified using powder X-ray diffraction technique and scanning electron microscopy (SEM). Elemental composition and chemical state of the prepared samples were analyzed from the X-ray photoelectron spectroscopy (XPS). Considerable absorption in IR region was observed for Ho3+ doped Bi2O3 due to the electronic transitions of 5I8→5F4, 5I8→5F5, and 5I8→5I5, 5I6. The excellent ultra-violet (UV), white and infrared light (IR)-driven photocatalytic activity were suggested for pure and doped Bi2O3 samples. Ho3+-doped Bi2O3 micro-rods exhibits a better photocatalytic activity under white light irradiation. The consequence of the bandgap and the synergetic effect of Ho3+ and Bi2O3 on the photocatalytic degradation of MB were investigated.

Diurnal variation of O3, ClO, HOCl, HO2, and BrO observed by JEM/SMILES

NASA Astrophysics Data System (ADS)

Suzuki, Makoto; Mitsuda, Chihiro; Manago, Naohiro; Imai, Koji; Sakazaki, Takatoshi; Ozeki, Hiroyuki; Nishimoto, Eriko; Naito, Yoko; Akiyoshi, Hidehary; Kinnison, Douglas; Sano, Takuki; Shiotani, Masato

2013-04-01

SMILES; Superconducting Submillimeter-Wave Limb Emission Sounder is a 4 K cooled 625-650 GHz limb sounder to observe O3, HCl, ClO, HO2, HOCl, BrO, HNO3, and O3 isotopes. SMILES had been operated on the International Space Station from Oct. 12, 2009 to Apr. 21, 2010. Since ISS is 51° inclined orbit, 30-45 days SMILES zonal mean could provide diurnal variation of chemical species in the stratosphere and mesosphere. Diurnal variation of O3, ClO, HOCl, HO2, and BrO are compared with two nudged CGCM calculations (SD-WACCM; Specified-dynamics WACCM, and MIROC) and satellite observations. Diurnal variation of O3 agreed with SD-WACCM over 50-82 km, but small peak in the morning (7 am local time) is apparent for the SMILES but not for the SD-WACCM at 70 km. Diurnal variation of ClO agreed quite well between SMILES L2 ver. 2.2 and SD-WACCM from 19 to 76 km altitude region. But nighttime ClO value of SMILES L2 ver. 2,2 above 50 km is less than SD-WACCM (70%), which is not clearly explained by the SMILES retrieval issue or our current knowledge of chemical kinetics. Diurnal variation of HOCl also agreed quite nicely from 31 to 76 km. SMILES HOCl retrieval is difficult since it is strongly affected by nearby O3 isotope and O3 hot band lines, as well as very strong HCl line. The nighttime build up of HOCl observed SMILES at 44-68 km are nicely reproduced by the SD-WACCM calculation using JPL2006 chemical kinetics dataset. But chemical kinetics calculation using SMILES ClO, HO2, and HOCl at 35-45 km altitude supported much faster reaction rate of ClO + HO2 given by JPL2010. HO2 diurnal variation also agreed with SD-WACCM from 24 to 72 km. Above 76 km, SMILES L2 ver. 2.2 needs modification of a priori and its co-variance, and we will get better agreement with model calculations. SMILES L2 ver. 2.2 also shows night time bias due to AOS (Acousto-Optics Spectrometer) characteristics. SMILES Band C BrO observation is strongly interfered by overlapping O3 isotope lines, and it is

Trap Depth Engineering of SrSi2O2N2:Ln2+,Ln3+ (Ln2+ = Yb, Eu; Ln3+ = Dy, Ho, Er) Persistent Luminescence Materials for Information Storage Applications.

PubMed

Zhuang, Yixi; Lv, Ying; Wang, Le; Chen, Wenwei; Zhou, Tian-Liang; Takeda, Takashi; Hirosaki, Naoto; Xie, Rong-Jun

2018-01-17

Deep-trap persistent luminescence materials exhibit unique properties of energy storage and controllable photon release under additional stimulation, allowing for both wavelength and intensity multiplexing to realize high-capacity storage in the next-generation information storage system. However, the lack of suitable persistent luminescence materials with deep traps is the bottleneck of such storage technologies. In this study, we successfully developed a series of novel deep-trap persistent luminescence materials in the Ln 2+ /Ln 3+ -doped SrSi 2 O 2 N 2 system (Ln 2+ = Yb, Eu; Ln 3+ = Dy, Ho, Er) by applying the strategy of trap depth engineering. Interestingly, the trap depth can be tailored by selecting different codopants, and it monotonically increases from 0.90 to 1.18 eV in the order of Er, Ho, and Dy. This is well explained by the energy levels indicated in the host-referred binding energy scheme. The orange-red-emitting SrSi 2 O 2 N 2 :Yb,Dy and green-emitting SrSi 2 O 2 N 2 :Eu,Dy phosphors are demonstrated to be good candidates of information storage materials, which are attributed to their deep traps, narrow thermoluminescence glow bands, high emission efficiency, and excellent chemical stability. This work not only validates the suitability of deep-trap persistent luminescence materials in the information storage applications, but also broadens the avenue to explore such kinds of new materials for applications in anticounterfeiting and advanced displays.

Vertical Distribution of NO, NO(2), and HNO(3) as Derived from Stratospheric Absorption Infrared Spectra.

PubMed

Fontanella, J C; Girard, A; Gramont, L; Louisnard, N

1975-04-01

This paper is devoted to the results concerning NO, NO(2), and HNO(3) obtained during airborne experiments performed in June-July 1973 on Concorde 001. The altitude of flight was about 16 km. Results concerning NO are, within the accuracy of measurement, in agreement with results of a previousspectrometric balloonborne experiment conducted jointly by IASB and ONERA (14 May 1973). Nitric oxide is concentrated in stratospheric layers clearly above the flight altitude. Integrated amount of NO along the optical path is (4 +/- 1.5) x 10(16) mol cm(-2) for a solar elevation varying from +2 degrees above the horizontal plane to -1 degrees . A value of 6 x 10(8) mol cm(-3) may be given as an upper limit for the local concentration at the flight altitude. Thereis no significant difference in the integrated amount observed at sunset and sunrise. Measured value of NO(2) local concentration at 15.5 km is (1.1 +/- 0.2) x 10(9) mol cm(-3), in sunset conditions. This value is not greatly modified between 15 km and 30 km. Measured value of HNO(3). This value increases with altitude between 15 km and 20 km. The local concentration is maximum at 20 km. The measured value is (2 +/- 1) x 10(10) mol cm(-3) at 20 km. It seems that local concentration decreases rapidly above 20 km.

ESR and nonresonant microwave absorption of ErBa2Cu3O(7-delta) and HoBa2Cu3O(7-delta) single crystals

NASA Astrophysics Data System (ADS)

Tagaya, Kimihito; Fukuoka, Nobuo; Nakanishi, Shigemitsu

1990-12-01

ESR measurements were performed for ErBa2Cu3O(7-delta) and HoBa2Cu3O(7-delta) single crystals from 77 K to room temperature. The ESR signals of Er2BaCuO5 and Ho2BaCuO5 were observed, and their temperature variations were investigated. Nonresonant microwave absorption was also observed below the superconducting critical temperature of 93 K. The principal values of lower critical field were determined.

Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175-200 K

NASA Astrophysics Data System (ADS)

Iannarelli, Riccardo; Rossi, Michel J.

2016-09-01

Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175-200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 / H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 / H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and

X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

NASA Technical Reports Server (NTRS)

Romanova, A. V.; Skryshevskiy, A. F.

1979-01-01

Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

Raman study of HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) superconductors

NASA Astrophysics Data System (ADS)

Zhou, Xingjiang; Cardona, M.; Chu, C. W.; Lin, Q. M.; Loureiro, S. M.; Marezio, M.

1996-02-01

Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) high- Tc superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm -1, with increasing number of CuO 2 layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm -1 mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm -1 mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm -1 modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.

Development of an airborne three-channel LED-based broadband cavity enhanced absorption spectrometer: towards an improved understanding of nighttime chemistry of NO3 and N2O5 in northwest Europe

NASA Astrophysics Data System (ADS)

Ouyang, Bin

2015-04-01

A three-channel cavity-enhanced absorption spectrometer capable of covering a broad UV-vis spectrum range has been developed in Cambridge for deployment on board the UK FAAM BAe-146 atmospheric research aircraft for measuring in situ concentrations of important atmospheric absorbers such as NO3, N2O5, NO2, IO and H2O and also aerosol extinction. So far this instrument has been deployed in two aircraft campaigns (the ROle of Nighttime chemistry in controlling the Oxidative Capacity of the atmOsphere, RONOCO, during July 2010 and January 2011; and the Coordinated Airborne Studies in the Tropics, CAST, during February 2014) with focuses on measuring NO2/NO3/N2O5 (for RONOCO) and IO (for CAST). In this talk, I will start by briefly presenting the working principle, design consideration, sensitivity test as well as intercomparison results of this novel aircraft instrument. I will then move on to present recent results from the analysis of the RONOCO campaign data, to illustrate the spatial and temporal variability of nighttime chemistry processes revealed by the high-resolution NO3 and N2O5 data collected. Significant improvements were made towards a better understanding of the oxidation of reactive VOCs by NO3 and O3 and the contribution of peroxy radicals (HO2 and RO2, of which only HO2 was successfully measured) to NO3 direct losses, and towards determining factors (organics and nitrate components of the aerosol particles, and relative humidity) that greatly influence the rate of N2O5 uptake by aerosol particles as well as directly probing the role of cloud, rain and ice scavenging in removing N2O5, in this typical northwest European environment.

Tris(5,6-dimethyl-1H-benzimidazole-κN 3)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)nickel(II)

PubMed Central

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-01-01

The title mononuclear complex, [Ni(C7H3NO4)(C9H10N2)3], shows a central NiII atom which is coordinated by two carboxyl­ate O atoms and the N atom from a pyridine-2,6-dicarboxyl­ate ligand and by three N atoms from different 5,6-dimethyl-1H-­benzimidazole ligands in a distorted octa­hedral geometry. The crystal structure shows intermolecular N—H⋯O hydrogen bonds. PMID:22719301

Optical properties of Mg2+, Yb3+, and Ho3+ tri-doped LiNbO3 crystals

NASA Astrophysics Data System (ADS)

Dai, Li; Liu, Chun-Rui; Tan, Chao; Yan, Zhe-Hua; Xu, Yu-Heng

2017-04-01

A series of LiNbO3 crystals tri-doped with Mg{}2+, Yb{}3+, and Ho{}3+ are grown by the conventional Czochraski technique. The concentrations of Mg{}2+, Yb{}3+, and Ho{}3+ ions in Mg:Yb:Ho:LiNbO3 crystals are measured by using an inductively coupled plasma atomic emission spectrometry. The x-ray diffraction is proposed to determine the lattice constant and analyze the internal structure of the crystal. The light-induced scattering of Mg:Yb:Ho:LiNbO3 crystal is quantitatively described via the threshold effect of incident exposure energy flux. The exposure energy ({E}{{r}}) is calculated to discuss the optical damage resistance ability. The exposure energy of Mg(7 mol):Yb:Ho:LiNbO3 crystal is 709.17 J/cm2, approximately 425 times higher than that of the Mg(1 mol):Yb:Ho:LiNbO3 crystal in magnitude. The blue, red, and very intense green bands of Mg:Yb:Ho:LiNbO3 crystal are observed under the 980-nm laser excitation to evaluate the up-conversion emission properties. The dependence of the emission intensity on pumping power indicates that the up-conversion emission is a two-photon process. The up-conversion emission mechanism is discussed in detail. This study indicates that Mg:Yb:Ho:LiNbO3 crystal can be applied to the fabrication of new multifunctional photoluminescence devices. Project supported by the National Natural Science Foundation of China (Grant No. 51301055), the Youth Science Fund of Heilongjiang Province, China (Grant No. QC2015061), the Special Funds of Harbin Innovation Talents in Science and Technology Research, China (Grant No. 2015RQQXJ045 ), and the Science Funds for the Young Innovative Talents of Harbin University of Science and Technology, China (Grant No. 201501).

Two basic bismuth nitrates: [Bi6O6(OH)2](NO3)4 · 2H2O with superior photodegradation activity for rhodamine B and [Bi6O5(OH)3](NO3)5 · 3H2O with ultrahigh adsorption capacity for methyl orange

NASA Astrophysics Data System (ADS)

Pang, Jiawei; Han, Qiaofeng; Liu, Weiqi; Shen, Zichen; Wang, Xin; Zhu, Junwu

2017-11-01

A novel basic bismuth nitrate, [Bi6O6(OH)2](NO3)4·2H2O (denoted as BiON-4N), was easily obtained at room temperature in the existence of 2-methoxyethanol (CH3OCH2CH2OH; 2ME) with a pH value ranging from 4.5 to 7.0. The morphology of BiON-4N could be easily tailored by changing the variety and amount of bases like urea, hexamethylenetetramine (HMTA), NaOH and NH3·H2O. When the solution pH was decreased lower than 4.5, another basic bismuth nitrate, [Bi6O5(OH)3](NO3)5·3H2O (denoted as BiON-5N), could be synthesized. Among those, BiON-4N nanoparticles obtained with 40 mmol of HMTA exhibited superior photocatalytic activity for rhodamine B (RhB) degradation with an efficiency of 100% within 4 min of UV light irradiation, which was much higher than that of commercial TiO2 (P25). The excellent photocatalytic performance of BiON-4N was mainly attributed to higher surface area (13.1 m2 g-1) in comparison with other basic bismuth nitrates. Furthermore, the as-prepared BiON-5N revealed excellent adsorption performance for the anions like methyl orange (MO) and K2Cr2O7, and especially for MO, the maximum adsorption capacity arrived up to 730 mg g-1, which should be relevant to highly positively charged surface. This work provides a new strategy for developing bismuth-based nanomaterials in the big bismuth family as potential photocatalyst and adsorbent for the removal of dyes and contaminants.

Aqua­(dicyanamido-κN 1)(nitrato-κ2 O,O′)(2,3,5,6-tetra-2-pyridylpyrazine-κ3 N 2,N 1,N 6)manganese(II)

PubMed Central

Callejo, Lorena; De la Pinta, Noelia; Vitoria, Pablo; Cortés, Roberto

2009-01-01

In the title compound, [Mn(C2N3)(NO3)(C24H16N6)(H2O)], the central manganese(II) ion is hepta­coordinated to a tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligand (tppz), a bidentate nitrate ligand, a terminal monodentate dicyanamide ligand (dca) and a water mol­ecule. The structure contains isolated neutral complexes, which are linked by O(water)—H⋯N hydrogen bonds generating chains along [010]. PMID:21581535

The influence of NH3 on NO2 conversion in a dc corona discharge in N2:O2:CO2:NO2:NH3 mixture

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy; Czech, Tadeusz; Konieczka, Jerzy

1996-10-01

The aim of this paper is to investigate the influence of NH3 additive (540-1470 ppm) on the conversion of NO2 and the creation of NO and N2O in a mixture of N2:O2:CO2: NO2:NH3 subjected to the so-called direct current (dc) corona discharge. The dc corona discharge was generated in a needle-to-plate reactor. Seven positively polarized needles were used as one electrode and a stainless steel plate as the other. The time-averaged discharge current was varied from 0 to 7 mA. It was found that the dc corona discharge decomposed NO2 and produced NO and N2O. The reduction of NO2 was higher without NH3 additive if the residence time of the operating gas was relatively short. However, in a longer corona discharge processing the NH3 additive may be useful for reduction of NO2.

Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

NASA Astrophysics Data System (ADS)

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

2017-06-01

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Controlled Nitric Oxide Production via O(1D) + N2O Reactions for Use in Oxidation Flow Reactor Studies

NASA Technical Reports Server (NTRS)

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John;

Heterogeneous interaction of SiO2 with N2O5: aerosol flow tube and single particle optical levitation-Raman spectroscopy studies.

PubMed

Tang, M J; Camp, J C J; Rkiouak, L; McGregor, J; Watson, I M; Cox, R A; Kalberer, M; Ward, A D; Pope, F D

2014-09-25

Silica (SiO2) is an important mineral present in atmospheric mineral dust particles, and the heterogeneous reaction of N2O5 on atmospheric aerosol is one of the major pathways to remove nitrogen oxides from the atmosphere. The heterogeneous reaction of N2O5 with SiO2 has only been investigated by two studies previously, and the reported uptake coefficients differ by a factor of >10. In this work two complementary laboratory techniques were used to study the heterogeneous reaction of SiO2 particles with N2O5 at room temperature and at different relative humidities (RHs). The uptake coefficients of N2O5, γ(N2O5), were determined to be (7.2 ± 0.6) × 10(-3) (1σ) at 7% RH and (5.3 ± 0.8) × 10(-3) (1σ) at 40% RH for SiO2 particles, using the aerosol flow tube technique. We show that γ(N2O5) determined in this work can be reconciled with the two previous studies by accounting for the difference in geometric and BET derived aerosol surface areas. To probe the particle phase chemistry, individual micrometer sized SiO2 particles were optically levitated and exposed to a continuous flow of N2O5 at different RHs, and the composition of levitated particles was monitored online using Raman spectroscopy. This study represents the first investigation into the heterogeneous reactions of levitated individual SiO2 particles as a surrogate for mineral dust. Relative humidity was found to play a critical role: while no significant change of particle composition was observed by Raman spectroscopy during exposure to N2O5 at RH of <2%, increasing the RH led to the formation of nitrate species on the particle surface which could be completely removed after decreasing the RH back to <2%. This can be explained by the partitioning of HNO3 between the gas and adsorbed phases. The atmospheric implications of this work are discussed.

Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

PubMed

Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

2001-02-01

The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

NASA Technical Reports Server (NTRS)

Anderson, James G.

1999-01-01

Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

Controlled nitric oxide production via O( 1D)+N 2O reactions for use in oxidation flow reactor studies

DOE PAGES

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; ...

2017-06-22

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O 3) is photolyzed at 254 nm to produce O( 1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O 3 hinders the ability of oxidation flow reactors to simulate NO x-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NO x (NO+NO 2) to nitric acid (HNO 3), making it impossible to sustain NOmore » x at levels that are sufficient to compete with hydroperoxy (HO 2) radicals as a sink for organic peroxy (RO 2) radicals. We developed a new method that is well suited to the characterization of NO x-dependent SOA formation pathways in oxidation flow reactors. NO and NO 2 are produced via the reaction O( 1D) + N 2O → 2NO, followed by the reaction NO + O 3 → NO 2+O 2. Laboratory measurements coupled with photochemical model simulations suggest that O( 1D) + N 2O reactions can be used to systematically vary the relative branching ratio of RO 2 + NO reactions relative to RO 2 + HO 2 and/or RO 2 + RO 2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO 3 -) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NO x-influenced environments and in laboratory chamber experiments.« less

Controlled nitric oxide production via O( 1D)+N 2O reactions for use in oxidation flow reactor studies

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

Lambe, Andrew; Massoli, Paola; Zhang, Xuan

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O 3) is photolyzed at 254 nm to produce O( 1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O 3 hinders the ability of oxidation flow reactors to simulate NO x-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NO x (NO+NO 2) to nitric acid (HNO 3), making it impossible to sustain NOmore » x at levels that are sufficient to compete with hydroperoxy (HO 2) radicals as a sink for organic peroxy (RO 2) radicals. We developed a new method that is well suited to the characterization of NO x-dependent SOA formation pathways in oxidation flow reactors. NO and NO 2 are produced via the reaction O( 1D) + N 2O → 2NO, followed by the reaction NO + O 3 → NO 2+O 2. Laboratory measurements coupled with photochemical model simulations suggest that O( 1D) + N 2O reactions can be used to systematically vary the relative branching ratio of RO 2 + NO reactions relative to RO 2 + HO 2 and/or RO 2 + RO 2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO 3 -) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NO x-influenced environments and in laboratory chamber experiments.« less

Simple sonochemical synthesis of Ho2O3-SiO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminant.

PubMed

Zinatloo-Ajabshir, Sahar; Mortazavi-Derazkola, Sobhan; Salavati-Niasari, Masoud

2017-11-01

In this work, highly photocatalytically active Ho 2 O 3 -SiO 2 nanocomposites have been designed and applied for decomposition of methylene blue pollutant. Ho 2 O 3 -SiO 2 nanocomposites have been produced by new, quick and facile sonochemical process with the aid of tetramethylethylenediamine as a novel basic agent for the first time. The effect of the kind of basic agent, ultrasonic time and dosage of Ho source on the grain size, photocatalytic behavior and shape of the Ho 2 O 3 -SiO 2 nanocomposites have been evaluated for optimization the production condition. FESEM, EDX, FT-IR, DRS, XRD and TEM have been applied to characterize the as-produced Ho 2 O 3 -SiO 2 nanocomposites. Use of the as-produced Ho 2 O 3 -SiO 2 nanocomposites as photocatalyst via destruction of methylene blue pollutant under UV illumination has been compared. It was observed that SiO 2 has notable impact on catalytic activity of holmium oxide photocatalyst for destruction. Introducing of SiO 2 to holmium oxide can enhance destruction efficiency of holmium oxide to methylene blue pollutant under ultraviolet light. Copyright © 2017 Elsevier B.V. All rights reserved.

Atmospheric chemistry of C 2F 5CHO: reaction with Cl atoms and OH radicals, IR spectrum of C 2F 5C(O)O 2NO 2

NASA Astrophysics Data System (ADS)

Sulbaek Andersen, M. P.; Hurley, M. D.; Wallington, T. J.; Ball, J. C.; Martin, J. W.; Ellis, D. A.; Mabury, S. A.; Nielsen, O. J.

2003-09-01

Smog chamber/FTIR techniques were used to measure k(Cl + C 2F 5CHO)=(1.96 ± 0.28) × 10 -12 and k(OH + C 2F 5CHO)=(5.26 ± 0.80) × 10 -13 cm 3 molecule -1 s -1 in 700 Torr of N 2 or air at 296 ± 2 K. The Cl initiated oxidation of C 2F 5CHO in the presence of NO in air diluent gave COF 2, CF 3ONO 2, and C 2F 5C(O)O 2NO 2 in molar yields of 180 ± 19%, 6.1 ± 0.6%, and 1.0 ± 0.3%, respectively. The IR spectrum for C 2F 5C(O)O 2NO 2 is reported. Results are discussed with respect to the potential for the atmospheric degradation of fluorinated aldehydes, C nF 2 n+1 CHO, to contribute to the observed environmental burden of fluorinated carboxylic acids, C nF 2 n+1 C(O)OH.

Some aspects of stratospheric chemical response to solar particle precipitations. I - Potential roles of N2/A3Sigma/ and ion-chemistry

NASA Technical Reports Server (NTRS)

Prasad, S. S.

1979-01-01

Large amounts of long lived N2(A3Sigma) are created by the energy degradation of precipitating solar particles. Laboratory data suggest that in the stratosphere N2(A3Sigma) are efficiently converted into N2O. Through reactions with O(1D), N2O may gradually release NO and thereby influence the long term aspects of stratospheric chemical response. During the daytime, negative ions may transform an active NO(x) into an inactive HNO3. At night both negative and positive ion chemistry generate HO(x). Omission of ionic chemistry results in considerable underestimation of O3 depletion during the initial phases of solar particle events, and thereby introduces significant error in the estimation of the nature of the prompt response.

Ab initio electron correlated studies on the intracluster reaction of NO+ (H2O)(n) → H3O+ (H2O)(n-2) (HONO) (n = 4 and 5).

PubMed

Asada, Toshio; Nagaoka, Masataka; Koseki, Shiro

2011-01-28

Hydrated nitrosonium ion clusters NO(+)(H(2)O)(n) (n = 4 and 5) were investigated by using MP2/aug-cc-pVTZ level of theory to clarify isomeric reaction pathways for formation of HONO and fully hydrated hydride ions. We found some new isomers and transition state structures in each hydration number, whose lowest activation energies of the intracluster reactions were found to be 4.1 and 3.4 kcal mol(-1) for n = 4 and n = 5, respectively. These thermodynamic properties and full quantum mechanical molecular dynamics simulation suggest that product isomers with HONO and fully hydrated hydride ions can be obtained at n = 4 and n = 5 in terms of excess hydration binding energies which can overcome these activation barriers.

Uptake of HNO3 on aviation kerosene and aircraft engine soot: influences of H2O or/and H2SO4.

PubMed

Loukhovitskaya, Ekaterina E; Talukdar, Ranajit K; Ravishankara, A R

2013-06-13

The uptake of HNO3 on aviation kerosene soot (TC-1 soot) was studied in the absence and presence of water vapor at 295 and 243 K. The influence of H2SO4 coating of the TC-1 soot surface on HNO3 uptake was also investigated. Only reversible uptake of HNO3 was observed. HONO and NO2, potential products of reactive uptake of HNO3, were not observed under any conditions studied here. The uptake of nitric acid increased slightly with relative humidity (RH). Coating of the TC-1 soot surface with sulfuric acid decreased the uptake of HNO3 and did not lead to displacement of H2SO4 from the soot surface. A limited set of measurements was carried out on soot generated by aircraft engine combustor (E-soot) with results similar to those on TC-1 soot. The influence of water on HNO3 uptake on E-soot appeared to be more pronounced than on TC-1 soot. Our results suggest that HNO3 loss in the upper troposphere due to soot is not significant except perhaps in aircraft exhaust plumes. Our results also suggest that HNO3 is not converted to either NO2 or HONO upon its uptake on soot in the atmosphere.

Heterogeneous Nitration of Tyrosine by NO­3 and N2O5: Rates, Mechanisms and Product Yields

NASA Astrophysics Data System (ADS)

Talukdar, R. K.; Witkowski, B.; Burkholder, J. B.; Roberts, J. M.

2015-12-01

Nitration of protein-bound tyrosine has been identified as a casual connection between air pollution and human health. Tyrosine is a common amino acid, 4-hydroxyphenylalanine, HO-C6H4-CH2-CH(NH2)-C(O)OH), and is present in many atmospheric bio-aerosols. Nitration of the aromatic units of protein molecules in polluted air enhances their allergenicity. The mechanism of heterogeneous nitration process of bio-aerosols by common nitrating agents in the atmosphere, O3/NO2, NO3, N2O5 is not well understood. This chemistry is thought to proceed via reactions with O3 and NO2 on particle surfaces, through mechanisms that are still uncertain. The possible role of higher nitrogen oxides also remains uncertain, partly due to a lack of measurements of fundamental chemical and physical parameters. In this work, we undertook measurements of reactive uptake of NO3, N2O5, as a function of relative humidity and temperature in a tyrosine coated flow tube reactor with chemical ionization mass spectrometric (CIMS) detection. Uptake coefficients on tyrosine coated flow tube were small under low relative humidity but were enhanced by an order of magnitude in the presence of high relative humidity, particularly for N2O5. The measured uptake coefficients were mostly due to reaction with water adsorbed on the surface of the flow tube. Only ~10% of the reactive uptake could be attributed to reaction with tyrosine. Following uptake, the contents of the flow tube were extracted, and analyzed using electrospray ionization - mass spectrometer (ESI-MS) to identify and quantify the products of the nitration reaction. The only organic reaction product detected was 3-nitro-tyrosine (3-NT). The measured uptake coefficients, mechanism of the title reactions and the possible atmospheric implications of these findings will be discussed.

Global CO emission estimates inferred from assimilation of MOPITT and IASI CO data, together with observations of O3, NO2, HNO3, and HCHO.

NASA Astrophysics Data System (ADS)

Zhang, X.; Jones, D. B. A.; Keller, M.; Jiang, Z.; Bourassa, A. E.; Degenstein, D. A.; Clerbaux, C.; Pierre-Francois, C.

2017-12-01

Atmospheric carbon monoxide (CO) emissions estimated from inverse modeling analyses exhibit large uncertainties, due, in part, to discrepancies in the tropospheric chemistry in atmospheric models. We attempt to reduce the uncertainties in CO emission estimates by constraining the modeled abundance of ozone (O3), nitrogen dioxide (NO2), nitric acid (HNO3), and formaldehyde (HCHO), which are constituents that play a key role in tropospheric chemistry. Using the GEOS-Chem four-dimensional variational (4D-Var) data assimilation system, we estimate CO emissions by assimilating observations of CO from the Measurement of Pollution In the Troposphere (MOPITT) and the Infrared Atmospheric Sounding Interferometer (IASI), together with observations of O3 from the Optical Spectrograph and InfraRed Imager System (OSIRIS) and IASI, NO2 and HCHO from the Ozone Monitoring Instrument (OMI), and HNO3 from the Microwave Limb Sounder (MLS). Our experiments evaluate the inferred CO emission estimates from major anthropogenic, biomass burning and biogenic sources. Moreover, we also infer surface emissions of nitrogen oxides (NOx = NO + NO2) and isoprene. Our results reveal that this multiple species chemical data assimilation produces a chemical consistent state that effectively adjusts the CO-O3-OH coupling in the model. The O3-induced changes in OH are particularly large in the tropics. Overall, our analysis results in a better constrained tropospheric chemical state.

Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

PubMed Central

González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

2017-01-01

The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy

1996-10-01

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO2 and N2O in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm3/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N2:O2:CO2 mixture the corona discharge produced NO, NO2 and N2O. In the N2:O2:CO2:NO2 mixture the reduction of NO2 was between 6-56%, depending on the concentration of O2, gas flow rate and corona discharge current. The NO2 reduction was accompanied by production of NO and N2O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N2 and O2 if reducing additives are not employed.

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

1993-01-01

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

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.

Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

PubMed

Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

2007-02-15

In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

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

Uptake of CO2, SO2, HNO3 and HCl on calcite (CaCO3) at 300 K: mechanism and the role of adsorbed water.

PubMed

Santschi, Ch; Rossi, M J

2006-06-01

All experimental observations of the uptake of the four title compounds on calcite are consistent with the presence of a reactive bifunctional surface intermediate Ca(OH)(HCO3) that has been proposed in the literature. The uptake of CO2 and SO2 occurs on specific adsorption sites of crystalline CaCO3(s) rather than by dissolution in adsorbed water, H2O(ads). SO2 primarily interacts with the bicarbonate moiety whereas CO2, HNO3 and HCl all react first with the hydroxyl group of the surface intermediate. Subsequently, the latter two react with the bicarbonate group to presumably form Ca(NO3)2 and CaCl2.2H2O. The effective equilibrium constant of the interaction of CO2 with calcite in the presence of H2O(ads) is kappa = deltaCO2/(H2O(ads)[CO2]) = 1.62 x 10(3) bar(-1), where CO2 is the quantity of CO2 adsorbed on CaCO3. The reaction mechanism involves a weakly bound precursor species that is reversibly adsorbed and undergoes rate-controlling concurrent reactions with both functionalities of the surface intermediate. The initial uptake coefficients gamma0 on calcite powder depend on the abundance of H2O(ads) under the present experimental conditions and are on the order of 10(-4) for CO2 and 0.1 for SO2, HNO3 and HCl, with gamma(ss) being significantly smaller than gamma0 for HNO3 and HCl, thus indicating partial saturation of the uptake. At 33% relative humidity and 300 K there are 3.5 layers of H2O adsorbed on calcite that reduce to a fraction of a monolayer of weakly and strongly bound water upon pumping and/or heating.

A pilot study of gaseous pollutants' measurement (NO2, SO2, NH3, HNO3 and O3) in Abidjan, Côte d'Ivoire: contribution to an overview of gaseous pollution in African cities

NASA Astrophysics Data System (ADS)

Bahino, Julien; Yoboué, Véronique; Galy-Lacaux, Corinne; Adon, Marcellin; Akpo, Aristide; Keita, Sékou; Liousse, Cathy; Gardrat, Eric; Chiron, Christelle; Ossohou, Money; Gnamien, Sylvain; Djossou, Julien

2018-04-01

This work is part of the DACCIWA FP7 project (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) in the framework of the Work Package 2 Air Pollution and Health. This study aims to characterize urban air pollution levels through the measurement of NO2, SO2, NH3, HNO3 and O3 in Abidjan, the economic capital of Côte d'Ivoire. Measurements of inorganic gaseous pollutants, i.e. NO2, SO2, NH3, HNO3 and O3 were performed in Abidjan during an intensive campaign within the dry season (15 December 2015 to 16 February 2016), using INDAAF (International Network to study Deposition and Atmospheric chemistry in AFrica) passive samplers exposed in duplicate for 2-week periods. Twenty-one sites were selected in the district of Abidjan to be representative of various anthropogenic and natural sources of air pollution in the city. Results from this intensive campaign show that gas concentrations are strongly linked to surrounding pollution sources and show a high spatial variability. Also, NH3, NO2 and O3 gases were present at relatively higher concentrations at all the sites. NH3 average concentrations varied between 9.1 ± 1.7 ppb at a suburban site and 102.1 ± 9.1 ppb at a domestic fires site. NO2 mean concentration varied from 2.7 ± 0.1 ppb at a suburban site to 25.0 ± 1.7 ppb at an industrial site. Moreover, we measured the highest O3 concentration at the two coastal sites of Gonzagueville and Félix-Houphouët-Boigny International Airport located in the southeast of the city, with average concentrations of 19.1 ± 1.7 and 18.8 ± 3.0 ppb, respectively. The SO2 average concentration never exceeded 7.2 ± 1.2 ppb over all the sites, with 71.5 % of the sampling sites showing concentrations ranging between 0.4 and 1.9 ppb. The HNO3 average concentration ranged between 0.2 and 1.4 ppb. All these results were combined with meteorological parameters to provide the first mapping of gaseous pollutants on the scale of the district of Abidjan using geostatistical

(Carbonato-κ(2)O,O')bis-(5,5'-dimethyl-2,2'-bipyridyl-κ(2)N,N')cobalt(III) bromide trihydrate.

PubMed

Arun Kumar, Kannan; Meera, Parthsarathi; Amutha Selvi, Madhavan; Dayalan, Arunachalam

2012-04-01

In the title complex, [Co(CO(3))(C(12)H(12)N(2))(2)]Br·3H(2)O, the Co(III) cation has a distorted octa-hedral coordination environment. It is chelated by four N atoms of two different 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water mol-ecules are disordered and their H atoms were not located, there are typical O⋯O distances between 2.8 and 3.0 Å, indicating O-H⋯O hydrogen bonding. The crystal packing is consolidated by C-H⋯O and C-H⋯Br hydrogen bonds, as well as π-π stacking inter-actions between adjacent pyridine rings of the dmbpy ligands, with centroid-centroid distances of 3.694 (3) and 3.7053 (3) Å.

Production of N2O5 and ClNO2 through Nocturnal Processing of Biomass-Burning Aerosol.

PubMed

Ahern, Adam T; Goldberger, Lexie; Jahl, Lydia; Thornton, Joel; Sullivan, Ryan C

2018-01-16

Biomass burning is a source of both particulate chloride and nitrogen oxides, two important precursors for the formation of nitryl chloride (ClNO 2 ), a source of atmospheric oxidants that is poorly prescribed in atmospheric models. We investigated the ability of biomass burning to produce N 2 O 5 (g) and ClNO 2 (g) through nocturnal chemistry using authentic biomass-burning emissions in a smog chamber. There was a positive relationship between the amount of ClNO 2 formed and the total amount of particulate chloride emitted and with the chloride fraction of nonrefractory particle mass. In every fuel tested, dinitrogen pentoxide (N 2 O 5 ) formed quickly, following the addition of ozone to the smoke aerosol, and ClNO 2 (g) production promptly followed. At atmospherically relevant relative humidities, the particulate chloride in the biomass-burning aerosol was rapidly but incompletely displaced, likely by the nitric acid produced largely by the heterogeneous uptake of N 2 O 5 (g). Despite this chloride acid displacement, the biomass-burning aerosol still converted on the order of 10% of reacted N 2 O 5 (g) into ClNO 2 (g). These experiments directly confirm that biomass burning is a potentially significant source of atmospheric N 2 O 5 and ClNO 2 to the atmosphere.

Ho3+-doped AlF3-TeO2-based glass fibers for 2.1 µm laser applications

NASA Astrophysics Data System (ADS)

Wang, S. B.; Jia, Z. X.; Yao, C. F.; Ohishi, Y.; Qin, G. S.; Qin, W. P.

2017-05-01

Ho3+-doped AlF3-TeO2-based glass fibers based on AlF3-BaF2-CaF2-YF3-SrF2-MgF2-TeO2 glasses are fabricated by using a rod-in-tube method. The glass rod including a core and a thick cladding layer is prepared by using a suction method, where the thick cladding layer is used to protect the core from the effect of surface crystallization during the fiber drawing. By inserting the glass rod into a glass tube, the glass fibers with relatively low loss (~2.3 dB m-1 @ 1560 nm) are prepared. By using a 38 cm long Ho3+-doped AlF3-TeO2-based glass fiber as the gain medium and a 1965 nm fiber laser as the pump source, 2065 nm lasing is obtained for a threshold pump power of ~220 mW. With further increasing the pump power to ~325 mW, the unsaturated output power of the 2065 nm laser is about 82 mW and the corresponding slope efficiency is up to 68.8%. The effects of the gain fiber length on the lasing threshold, the slope efficiency, and the operating wavelength are also investigated. Our experimental results show that Ho3+-doped AlF3-TeO2-based glass fibers are promising gain media for 2.1 µm laser applications.

Vertical profiles of ClNO2 measured in Utah: dry deposition of N2O5 as a source of ClNO2

NASA Astrophysics Data System (ADS)

McLaren, Robert; Roberts, James M.; Kercher, James P.; Thornton, Joel A.; Brown, Steven S.; Edwards, Peter M.; Young, Cora Y.; Dube, William P.; Washenfelder, Rebecca A.; Williams, Eric J.; Holloway, John S.; Bates, Timothy S.; Quinn, Patricia K.

2013-04-01

Several recent observations of nitryl chloride (ClNO2) have suggested that this compound can accumulate to significant levels (several ppb) in the nocturnal boundary layer at night. Its photolytic loss the next day can be a significant source of chlorine atom radicals. The source of ClNO2 is known to be the heterogeneous reaction of N2O5 with aerosol chloride, not just confined to coastal regions but also observed thousands of kilometers inland in urban areas. During the Uintah Basin Winter Ozone Study (2012), we made measurements of ClNO2 by CIMS on a tower in a remote region of Utah where intensive natural gas extraction operations via hydraulic fracturing were occurring. Levels of ClNO2 were surprisingly high at night (up to 2 ppb) even though coastal aerosols were not present. Soils in the region were alkaline with high chloride content. To address the potential of N2O5 dry deposition as a source of ClNO2, we measured vertical profiles of ClNO2 from 1 to 12 m agl with a movable inlet. We observed negative gradients of ClNO2 and positive gradients of N2O5, which suggest that dry deposition of N2O5 and reaction with soil chloride as a source of ClNO2.

The Synthesis of a Core-Shell Photocatalyst Material YF3:Ho3+@TiO2 and Investigation of Its Photocatalytic Properties

PubMed Central

Xu, Xuan; Zhou, Shiyu; Long, Jun; Wu, Tianhu; Fan, Zihong

2017-01-01

In this paper, YF3:Ho3+@TiO2 core-shell nanomaterials were prepared by hydrolysis of tetra-n-butyl titanate (TBOT) using polyvinylpyrrolidone K-30 (PVP) as the coupling agent. Characterization methods including X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) under TEM, X-ray photoelectron spectroscopy (XPS), fluorescence spectrometry, ultraviolet-visible diffuse reflectance spectroscopy, and electron spin resonance (ESR) were used to characterize the properties and working mechanism of the prepared photocatalyst material. They indicated that the core phase YF3 nanoparticles were successfully coated with a TiO2 shell and the length of the composite was roughly 100 nm. The Ho3+ single-doped YF3:Ho3+@TiO2 displayed strong visible absorption peaks with wavelengths of 450, 537, and 644 nm, respectively. By selecting these three peaks as excitation wavelengths, we could observe 288 nm (5D4→5I8) ultraviolet emission, which confirmed that there was indeed an energy transfer from YF3:Ho3+ to anatase TiO2. In addition, this paper investigated the influences of different TBOT dosages on photocatalysis performance of the as-prepared photocatalyst material. Results showed that the YF3:Ho3+@TiO2 core-shell nanomaterial was an advanced visible-light-driven catalyst, which decomposed approximately 67% of rhodamine b (RhB) and 34.6% of phenol after 10 h of photocatalysis reaction. Compared with the blank experiment, the photocatalysis efficiency was significantly improved. Finally, the visible-light-responsive photocatalytic mechanism of YF3:Ho3+@TiO2 core-shell materials and the influencing factors of photocatalytic degradation were investigated to study the apparent kinetics, which provides a theoretical basis for improving the structural design and functions of this new type of catalytic material. PMID:28772662

Blue-shifted and red-shifted hydrogen bonds: Theoretical study of the CH3CHO· · ·HNO complexes

NASA Astrophysics Data System (ADS)

Yang, Yong; Zhang, Weijun; Gao, Xiaoming

The blue-shifted and red-shifted H-bonds have been studied in complexes CH3CHO?HNO. At the MP2/6-31G(d), MP2/6-31+G(d,p) MP2/6-311++G(d,p), B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels, the geometric structures and vibrational frequencies of complexes CH3CHO?HNO are calculated by both standard and CP-corrected methods, respectively. Complex A exhibits simultaneously red-shifted C bond H?O and blue-shifted N bond H?O H-bonds. Complex B possesses simultaneously two blue-shifted H-bonds: C bond H?O and N bond H?O. From NBO analysis, it becomes evident that the red-shifted C bond H?O H-bond can be explained on the basis of the two opposite effects: hyperconjugation and rehybridization. The blue-shifted C bond H?O H-bond is a result of conjunct C bond H bond strengthening effects of the hyperconjugation and the rehybridization due to existence of the significant electron density redistribution effect. For the blue-shifted N bond H?O H-bonds, the hyperconjugation is inhibited due to existence of the electron density redistribution effect. The large blue shift of the N bond H stretching frequency is observed because the rehybridization dominates the hyperconjugation.

The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

NASA Astrophysics Data System (ADS)

Iannarelli, R.; Rossi, M. J.

2015-11-01

Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

Stratospheric H2O and HNO3 profiles derived from solar occultation measurements

NASA Technical Reports Server (NTRS)

Fischer, H.; Fergg, F.; Rabus, D.; Burkert, P.

1985-01-01

Compact two-channel radiometers for solar occultation experiments have been constructed in order to measure stratospheric trace gases. The instruments can be used as filter- or correlation-type radiometers, depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the filter-type measurements, profiles of the trace gases H2O and HNO3 are inferred for the height region between the tropopause and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the trace gas profiles. The derived H2O and HNO3 profiles are assessed against the observations of other authors and are discussed in the light of the trace gas distributions calcualted from photochemical models.

Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

NASA Astrophysics Data System (ADS)

González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

2016-09-01

The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC] × [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 % < RH < 63 %) and of (4) the O2 / N2 ratio (15 % < O2 / N2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55 % RH and at ambient O2 / N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

Heterogeneous kinetics of N2O5 reactive uptake and chlorine activation in authentic biomass burning aerosol

NASA Astrophysics Data System (ADS)

Sullivan, R. C.; Jahl, L.; Goldberger, L.; Ahern, A.; Thornton, J. A.

2017-12-01

Nitryl chloride (ClNO2) is a nighttime reservoir of NOx that is formed from the uptake of dinitrogen pentoxide (N2O5) into particles containing chloride. The formation of ClNO2 from heterogeneous reactions of N2O5(g) with authentic biomass burning aerosol has not previously been studied. We observed the rapid production of N2O5 and then ClNO2 during dark chemical transformations of biomass burning aerosol produced from a variety of fuels using both a smog chamber and an aerosol flow tube reactor. Iodide adduct chemical ionization mass spectrometry was used to measure gas phase ClNO2 and N2O5, and acetate chemical ionization mass spectrometry to measure gaseous HCl and other compounds, while a soot particle aerosol mass spectrometer measured changes in aerosol composition as chloride was displaced by nitrate. Upon the addition of ozone to the biomass burning smoke, N2O5 was always rapidly formed and ClNO2 was subsequently detected in the gas phase. During experiments at high relative humidity, we observed decreases in particulate chloride and increases in particulate nitrate which we believe are due to acid displacement of HCl(g) by HNO3 since no additional ClNO2 was produced in the gas phase. The reactive uptake probability of N2O5 on authentic biomass burning aerosol and the yield of ClNO2 were determined for the first time using chamber and flow tube experiments on smoke from biomass fuels including sawgrass, giant cutgrass, palmetto leaves, and ponderosa pine. These experiments confirm the formation of N2O5 and ClNO2 in biomass burning emissions and suggest that biomass burning is a likely source of continental ClNO2 and HCl.

The uptake of HNO3 on meteoric smoke analogues

NASA Astrophysics Data System (ADS)

Frankland, Victoria L.; James, Alexander D.; Feng, Wuhu; Plane, John M. C.

2015-05-01

The uptake of HNO3, H2O, NO2 and NO was studied on meteoric smoke particle analogues using a low-pressure Knudsen cell operating at 295 K. The analogues used were olivine (MgFeSiO4) and a haematite/goethite (Fe2O3/FeO(OH)) mixture synthesised by the sol-gel process. For uptake on MgFeSiO4, the following uptake coefficients were obtained: γ(HNO3)=(1.8±0.3)×10-3, γ(H2O)=(4.0±1.3)×10-3, γ(NO2)=(5.7±0.2)×10-4 and γ(NO)<3×10-4. γ(HNO3) did not show a dependence on the mass of MgFeSiO4 in the Knudsen cell (when varied by a factor of 6) implying that, because of relatively efficient uptake, HNO3 is removed only by near-surface particles. This was corroborated by application of a surface uptake model. Saturating the MgFeSiO4 particles with water vapour before exposing them to NO2 increased γ(NO2) to (2.1±0.7)×10-3, but had a very small effect on γ(HNO3). For uptake on Fe2O3/FeO(OH), γ(HNO3)=(1.5±0.2)×10-3. These results were then included in a whole atmosphere chemistry-climate model, which shows that the heterogeneous removal on meteoric smoke particles in the winter polar vortex between 30 and 60 km appears to provide an important sink for HNO3.

CO from enhanced HO activity or from CORM-2 inhibits both O2- and NO production and downregulates HO-1 expression in LPS-stimulated macrophages.

PubMed

Srisook, Klaokwan; Han, Shan-Shu; Choi, Hyung-Sim; Li, Mei-Hua; Ueda, Hideo; Kim, Chaekyun; Cha, Young-Nam

2006-01-12

Carbon monoxide (CO) arising from heme degradation, catalyzed particularly by the stress-inducible heme oxygenase-1 (HO-1), has recently been demonstrated to provide cytoprotection against cell death in macrophages stimulated with bacterial lipopolysaccharide (LPS). In the present study, we determined the effects of CO on the production of reactive oxygen species (ROS) and nitric oxide (NO) by the LPS-stimulated RAW 264.7 macrophages. In addition, effect of CO-exposure on the production of superoxide (O(2)(-)) in the phorbol myristate acetate (PMA)-stimulated PLB-985 neutrophils was determined. Production of ROS by the LPS-stimulated macrophages pretreated with 50microM [Ru(CO)(3)Cl(2)](2), a CO-releasing molecule (CORM-2), was abolished and the production of O(2)(-) by the PMA-stimulated neutrophils pretreated with the CORM-2 was decreased markedly. The CORM-2 (50microM) was not cytotoxic to both the unstimulated and LPS-stimulated macrophages when determined by employing mitochondrial reductase function test (MTT assay). In macrophages pretreated with increasing doses of CORM-2, both the LPS-derived upregulations of iNOS (NO production) and HO-1 expression (CO production) were suppressed in a dose-dependent manner. Alternatively, when the macrophages were treated with LPS and CO-donor together, the LPS-derived increase in NO production was decreased. Conversely, when the control and LPS-stimulated macrophages were treated with zinc protoporphyrin IX (ZnPP) to inhibit the HO activity blocking endogenous production of CO (basal and enhanced), macrophages died extensively. Interestingly, production of NO in the LPS-stimulated macrophages increased significantly following the ZnPP treatment. Addition of CORM-2 to the LPS-treated cells that were being treated additionally with ZnPP did not prevent the cell death. However, endogenous overproduction of CO by super-induction of HO-1 (obtained by pretreatment of macrophages with either buthionine sulfoximine or hemin

Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

NASA Astrophysics Data System (ADS)

Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

2016-01-01

In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

Spectral properties and anti-Stokes luminescence of TeO2-BaF2:Ho3+, Ho3+/Yb3+ ceramics and glass excited by 1.9-μm radiation of a Tm:LiYF4 laser

NASA Astrophysics Data System (ADS)

Savikin, A. P.; Egorov, A. S.; Budruev, A. V.; Perunin, I. Yu.; Krasheninnikova, O. V.; Grishin, I. A.

2017-07-01

We demonstrate the up-conversion of Tm:LiYF4 infrared (IR) laser radiation with 1908-nm wavelength into visible light with a spectral maximum at 650 nm by ceramics with a composition of (100 - x)TeO2- xBaF2 - 1 wt % HoF3- yYbF3, where x = 20, 30, or 40 mol % and y = 0 or 0.5 wt %. The samples of 60TeO2-40BaF2 - 1 wt % HoF3 - 0.5 wt % YbF3 exhibited anti-Stokes luminescence at a threshold radiation power density of 1.0-1.5 W cm-2.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Tunable diode laser measurements of HO2NO2 absorption coefficients near 12.5 microns

NASA Technical Reports Server (NTRS)

May, R. D.; Molina, L. T.; Webster, C. R.

1988-01-01

A tunable diode laser spectrometer has been used to measure absorption coefficients of peroxynitric acid (HO2NO2) near the 803/cm Q branch. HO2NO2 concentrations in a low-pressure flowing gas mixture were determined from chemical titration procedures and UV absorption spectroscopy. The diode laser measured absorption coefficients, at a spectral resolution of better than 0.001/cm, are about 10 percent larger than previous Fourier transform infrared measurements made at a spectral resolution of 0.06/cm.

Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

NASA Technical Reports Server (NTRS)

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

1997-01-01

The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

Doping effect of nano-Ho{sub 2}O{sub 3} and naphthalene in MgB{sub 2} superconductor prepared by powder-in-sealed-tube method

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

Hansdah, J. S.; Sarun, P. M., E-mail: sarun.res@gmail.com

2015-03-21

The effect on crystal structure, critical temperature (T{sub C}), and critical current density (J{sub C}) of bulk MgB{sub 2} doped with nano-Ho{sub 2}O{sub 3} and naphthalene was studied. Among all the samples studied, the sample doped with 2.5 wt. % nano-Ho{sub 2}O{sub 3} have shown the best field dependent critical current density [J{sub C}(H)], i.e., 0.77 × 10{sup 5 }A/cm{sup 2} at 2 T and 10 K. While naphthalene doped MgB{sub 2} sample has shown the least J{sub C}(H) characteristics. The improved J{sub C}(H) characteristics in the nano-Ho{sub 2}O{sub 3} doped MgB{sub 2} samples are attributed to improved flux pinning properties due to the formation ofmore » HoB{sub 4} and in naphthalene doped MgB{sub 2} samples. The slight lower T{sub C} value (37.01 K) in naphthalene doped samples is attributed to the occurrence of lattice defect by the substitution of carbon at boron site of MgB{sub 2} superconductor. Lower ΔT{sub C} value implies the lesser anisotropy in all the synthesized samples. The flux pinning force density (F{sub P}/F{sub Pmax}) curves are theoretically analyzed using Dew-Hughes model. The result revealed that point pinning is the dominant pinning mechanism for nano-Ho{sub 2}O{sub 3} doped MgB{sub 2} samples, while, surface and grain boundary pinning become dominant with increasing naphthalene addition in nano-Ho{sub 2}O{sub 3} doped MgB{sub 2} samples.« less

Ab initio and transition state theory study of the OH + HO2 → H2O + O2(3Σg-)/O2(1Δg) reactions: yield and role of O2(1Δg) in H2O2 decomposition and in combustion of H2.

PubMed

Monge-Palacios, M; Sarathy, S Mani

2018-02-07

Reactions of hydroxyl (OH) and hydroperoxyl (HO 2 ) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO 2 → H 2 O + O 2 ( 3 Σ g - )/O 2 ( 1 Δ g ) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200-2500 K, represented by k(T) = 3.08 × 10 12 T 0.07  exp(1151/RT) + 8.00 × 10 12 T 0.32  exp(-6896/RT) and k(T) = 2.14 × 10 6 T 1.65  exp(-2180/RT) in cm 3 mol -1 s -1 , respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755-3772). The updated kinetic model was used to perform H 2 O 2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565-571), and to estimate flame speeds and ignition delay times in H 2 mixtures. The simulation predicted a larger amount of O 2 ( 1 Δ g ) in H 2 O 2 decomposition than that predicted by Konnov's original model. These differences in the O 2 ( 1 Δ g ) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H 2 O 2 decomposition and on the flame speeds and ignition delay times of different H 2 -oxidizer mixtures. However, if the oxidizer is seeded with O 3 , small differences appear in the flame speed. Given that O 2 ( 1 Δ g ) is much more reactive than O

Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

NASA Astrophysics Data System (ADS)

Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

2018-02-01

Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

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

PubMed

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

2015-02-26

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

Yields of O2(b 1 Sigma g +) from reactions of HO2. [in planetary atmospheres

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Choo, K. Y.; Leu, M. T.

1985-01-01

The production of O2(b 1 Sigma g +) has been monitored for several reactions of the HO2 radical at 300 K using a discharge-flow apparatus with resonance fluorescence and chemiluminescence detection. In all cases, the resulting quantum efficiencies were found to be less than 0.03. O2(b) was observed when F atoms were added to H2O2 in the gas phase. The signal strengths of O2(b) were proportional to initial concentrations of HO2 formed by the F + H2O2 reaction. Observed /O2(b)/, /HO2/, and /OH/ vs /F/0 were analyzed using a simple three-step mechanism and a more complete computer simulation with 22 reaction steps. The results indicate that the F + HO2 reaction yields O2(b) with an efficiency of (3.6 + or - 1.4) x 10 to the -3rd. Yields from the O + OH2 reaction were less than 0.02, indicating that this reaction cannot be a major source of the O2(b) emission observed in the earth's nightglow.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

PubMed

Rusanova, Julia A; Semenaka, Valentina V; Dyakonenko, Viktoriya V; Shishkin, Oleg V

2015-09-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands. The Cu(II) ion adopts a distorted square-pyramidal coordination while the Cr(III) ion has a distorted octa-hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O-H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two -CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1).

Vertical profiles of ClNO2 at a remote terrestrial site: evidence of N2O5 dry deposition as a source of ClNO2?

NASA Astrophysics Data System (ADS)

McLaren, R.; Roberts, J. M.; Kercher, J. P.; Thornton, J. A.; Brown, S. S.; Edwards, P. M.; Young, C. J.; Dube, W. P.; Washenfelder, R. A.; Williams, E. J.; Holloway, J. S.; Bates, T. S.; Quinn, P.

2012-12-01

Recent observations of nitryl chloride (ClNO2) have suggested that this compound can accumulate to significant levels (several ppb) in the nocturnal boundary layer at night. Its photolytic loss the next day can be a significant source of chlorine atom radicals. The source of ClNO2 is largely thought to be the heterogeneous reaction of N2O5 with aerosol chloride, not just confined to coastal regions but also observed thousands of kilometers inland in urban areas. During the Uintah Basin Winter Ozone Study, we made measurements of ClNO2 by CIMS on a tower in a remote region of Utah. Levels of ClNO2 were surprisingly high at night (up to 2 ppb) even though sea salt aerosols were not present. Soils in the region were alkaline with high chloride content. To address the potential of N2O5 dry deposition as a source of ClNO2, we measured vertical profiles of ClNO2 from 1 to 12 m agl with a movable inlet. We observed negative gradients of ClNO2 and positive gradients of nitrate (a surrogate for N2O5), which suggests that dry deposition of N2O5 and reaction with Cl- in soils is a source of ClNO2 in this region.

K2Ho(PO4)(WO4)

PubMed Central

Terebilenko, Katherina V.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Slobodyanik, Nikolay S.; Shishkin, Oleg V.

2008-01-01

A new compound, dipotassium holmium(III) phosphate(V) tungstate(VI), K2Ho(PO4)(WO4), has been obtained during investigation of the K2O–P2O5–WO3–HoF3 phase system using the flux technique. The compound is isotypic with K2Bi(PO4)(WO4). Its framework structure consists of flat ∞ 2[HoPO4] layers parallel to (100) that are made up of ∞ 1[HoO8] zigzag chains inter­linked via slightly distorted PO4 tetra­hedra. WO4 tetra­hedra are attached above and below these layers, leaving space for the K+ counter-cations. The HoO8, PO4 and WO4 units exhibit 2 symmetry. PMID:21580811

Insertion of bentonite with Organometallic [Fe3O(OOC6H5)6(H2O)3(NO3).nH2O] as Adsorbent of Congo Red

NASA Astrophysics Data System (ADS)

Said, Muhammad; Paluta Utami, Hasja; Hayati, Ferlina

2018-01-01

The adsorption of Congo red using bentonite inserted organometallic has been investigated. The insertion bentonite was characterized using FT-IR Spectrophotometer, XRD and XRF analysis. The FT-IR characterization showed the higher intensity of peak wavenumber at 470.6 cm-1 for Fe3O on the ratio 1:3. While the XRD characterization showed the shift of diffraction angle of 2θ was 5.2° and has a basal spacing of 16.8 Å. In the XRF characterization, the insertion process of organometallic occurred optimally with the percentage of metal oxide reached 71.75 %. The adsorption process of bentonite inserted organometallic compound [Fe3O(OOC6H5)6(H2O)3(NO3)·nH2O] showed the adsorption rate (k) is 0.050 min-1, the largest adsorption capacity (b) at 70°C is 4.48 mol/g, the largest adsorption energy at temperature 30°C which is 6.4 kJ/mol Organometallic compounds. The value of the enthalpy (ΔH) and entropy (ΔS) decreased with increasing concentrations of the Congo red. Effect of pH on the adsorption on at pH 3 shows the biggest of number Congo red absorbed is 19.52 mg/L for insertion of bentonite.

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

PubMed

Almond, Philip M; Albrecht-Schmitt, Thomas E

2002-10-21

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta

Bis[4-(4-pyridyl)pyridinium] (4-carboxy­pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)(pyridine-2,4,6-tricarboxyl­ato-κ3 O 2,N,O 6)ferrate(III) trihydrate

PubMed Central

Zhao, Li; Dong, You-Ren; Xie, Hong-Zhen

2009-01-01

In the title salt, (C10H9N2)2[Fe(C8H2NO6)(C8H3NO6)]·3H2O, the FeIII atom is O,N,O′-chelated by dianionic and trianionic ligands in a slightly distorted octa­hedral coordination geometry. The cations and ferrate anions are linked into a layered structure; the layers are connected through the uncoordinated water mol­ecules into a hydrogen-bonded three-dimensional supra­molecular structure. One of the uncoordinated water molecules is disordered around an inversion centre and was refined with half-occupancy for each position. PMID:21582387

Optical and Physical Investigations of Lanthanum Bismuth Borate glasses doped with Ho2O3

NASA Astrophysics Data System (ADS)

Ramesh, P.; Jagannath, G.; Eraiah, B.; Kokila, M. K.

2018-02-01

Holmium doped 10La2O3-15Bi2O3-(75-x) B2O3 (Ho3+: LBB) glasses have been prepared by melt quench technique and the impact of holmium ions concentration on optical and physical properties of present glasses have been examined. Ho3+ dependent density, molar volume, refractive index, rare earth ion concentration, polaron radius, inter ionic distance, field strength and energy band gap are calculated and tabulated. Amorphous nature of the all glasses has been confirmed by XRD patterns. The room temperature (RT) Uv-Vis absorption spectrum doped with 1 mol% of Ho2O3 exhibit eight prominent bands centred at 895, 641, 537, 486, 472, 467, 451 and 416 due to transition between ground state to various excited states. The results show that, the density is increases and molar volume of the glasses is decreases with an increase in Ho2O3 concentration and consequently generate more non-bridging oxygen (NBOs) in the glass matrix. The Urbach energy is increases with holmium concentration which exemplifies the degree of disorder present in the LBB glasses. The considerable increase in field strength observed in present glasses is attributed to occurrence of strong bridge between Ho3+ and B- ions and this strong bridge is possibly due to the displacement between Ho3+ and oxygen atoms which are generated from the conversion BO3-BO4 units.

Structural studies of Bi 2 O 3 -Nb 2 O 5 -TeO 2 glasses

DOE PAGES

Wilding, Martin C.; Delaizir, Gaelle; Benmore, Chris J.; ...

2016-07-25

Bi 2O 3-Nb 2O 5-TeO 2 glasses show unusual annealing behavior with appearance of spherulites within the matrix glass structure for the Bi 0.5Nb 0.5Te 3O 8 composition. The textures resemble those found previously among polyamorphic Al 2O 3-Y 2O 3 glasses containing metastably co-existing high- and low-density phases produced during quenching. However the spherulites produced within the Bi 2O 3-Nb 2O 5-TeO 2 glass are crystalline and can be identified as an “anti-glass” phase related to β-Bi 2Te 4O 11. Here, we used high energy synchrotron X-ray diffraction data to study structures of binary and ternary glasses quenched frommore » liquids within the Bi 2O 3-Nb 2O 5-TeO 2 system. These reveal a glassy network based on interconnected TeO 4 and TeO 3 units that is related to TeO 2 crystalline materials but with larger Te…Te separations due to the presence of TeO 3 groups and non-bridging oxygens linked to modifier (Bi 3 +, Nb 5 +) cations. Analysis of the viscosity-temperature relations indicates that the glass-forming liquids are “fragile” and there is no evidence for a LLPT occurring in the supercooled liquid. The glasses obtained by quenching likely correspond to a high-density amorphous (HDA) state. Subsequent annealing above T g shows mainly evidence for direct crystallization of the “anti-glass” tellurite phase. But, some evidence may exist for simultaneous formation of nanoscale amorphous spherulites that could correspond to the LDA polyamorph. The quenching and annealing behavior of Bi 2O 3-Nb 2O 5-TeO 2 supercooled liquids and glasses is compared with similar materials in the Al 2O 3-Y 2O 3 system.« less

Heterogeneous reaction of HO2 with airborne TiO2 particles and its implication for climate change mitigation strategies

NASA Astrophysics Data System (ADS)

Moon, Daniel R.; Taverna, Giorgio S.; Anduix-Canto, Clara; Ingham, Trevor; Chipperfield, Martyn P.; Seakins, Paul W.; Baeza-Romero, Maria-Teresa; Heard, Dwayne E.

2018-01-01

One geoengineering mitigation strategy for global temperature rises resulting from the increased concentrations of greenhouse gases is to inject particles into the stratosphere to scatter solar radiation back to space, with TiO2 particles emerging as a possible candidate. Uptake coefficients of HO2, γ(HO2), onto sub-micrometre TiO2 particles were measured at room temperature and different relative humidities (RHs) using an atmospheric pressure aerosol flow tube coupled to a sensitive HO2 detector. Values of γ(HO2) increased from 0.021 ± 0.001 to 0.036 ± 0.007 as the RH was increased from 11 to 66 %, and the increase in γ(HO2) correlated with the number of monolayers of water surrounding the TiO2 particles. The impact of the uptake of HO2 onto TiO2 particles on stratospheric concentrations of HO2 and O3 was simulated using the TOMCAT three-dimensional chemical transport model. The model showed that, when injecting the amount of TiO2 required to achieve the same cooling effect as the Mt Pinatubo eruption, heterogeneous reactions between HO2 and TiO2 would have a negligible effect on stratospheric concentrations of HO2 and O3.

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

The NO(x)-HNO3 System in the Lower Stratosphere: Insights from In Situ Measurements and Implications of the J(HNO3)-[OH] Relationship

NASA Technical Reports Server (NTRS)

Perkins, K. K.; Hanisco, T. F.; Cohen, R. C.; Koch, L. C.; Stimpfle, R. M.; Voss, P. B.; Bonne, G. P.; Lanzendorf, E. J.; Anderson, J. G.; Wennberg, P. O.

2001-01-01

During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18P(sub NOx)), which is within the measurement uncertainty of +/- 27%. The partitioning between NOx production processes is [HNO3 + OH (41 +/- 2)%; HNO3 + hv (59 +/- 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find: (1) the steady-state value of [NO2](sub 24h-avg)/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density; and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hv is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2](sub 24h-avg)/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2](sub 24h-avg)/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the

The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO3 + 2.5% Na2Cr2O7 solution

NASA Astrophysics Data System (ADS)

Savas, Terence P.; Wang, Allen Yi-Lan; Earthman, James C.

2003-04-01

The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO3 + 2.5% Na2Cr2O7 solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance ( Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm2, 4.2E + 08 Ω-cm2, and 3.7E + 04 Ω-cm2 for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm2 to 3.2E + 08 Ω-cm2 after 2 h exposures. The EIS response showed a polarization resistance ( R p) on the order of 6.6E + 04 Ω-cm2, 5.3E + 04 Ω-cm2, and 1.1E + 04 Ω-cm2 for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

PubMed

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

Testing fast photochemical theory during TRACE-P based on measurements of OH, HO2, and CH2O

NASA Astrophysics Data System (ADS)

Olson, Jennifer R.; Crawford, J. H.; Chen, G.; Fried, A.; Evans, M. J.; Jordan, C. E.; Sandholm, S. T.; Davis, D. D.; Anderson, B. E.; Avery, M. A.; Barrick, J. D.; Blake, D. R.; Brune, W. H.; Eisele, F. L.; Flocke, F.; Harder, H.; Jacob, D. J.; Kondo, Y.; Lefer, B. L.; Martinez, M.; Mauldin, R. L.; Sachse, G. W.; Shetter, R. E.; Singh, H. B.; Talbot, R. W.; Tan, D.

2004-08-01

Measurements of several short-lived photochemical species (e.g., OH, HO2, and CH2O) were obtained from the DC-8 and P3-B aircraft during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) campaign. To assess fast photochemical theory over the east Asian coast and western Pacific, these measurements are compared to predictions using a photochemical time-dependent box model constrained by coincident measurements of long-lived tracers and physical parameters. Both OH and HO2 are generally overpredicted by the model throughout the troposphere, which is a different result from previous field campaigns. The calculated-to-observed ratio of OH shows an altitude trend, with OH overpredicted by 80% in the upper troposphere and by 40-60% in the middle troposphere. Boundary layer and lower tropospheric OH ratios decrease from middle tropospheric values to 1.07 for the DC-8 and to 0.70 for the P3-B. HO2 measured on the DC-8 is overpredicted by a median of 23% and shows no trend in the agreement with altitude. Three subsets of data which compose 12% of the HO2 measurements represent outliers with respect to calculated-to-observed ratios: stratospherically influenced air, upper tropospheric data with NO > 135 pptv, and data from within clouds. Pronounced underpredictions of both HO2 and OH were found for stratospherically influenced air, which is in contrast to previous studies showing good agreement of predicted and observed HOx in the stratosphere. Observational evidence of heterogeneous uptake of HO2 within low and middle tropospheric clouds is presented, though there is no indication of significant HO2 uptake within higher-altitude clouds. Model predictions of CH2O are in good agreement with observations in the median for background concentrations, but a large scatter exists. Factors contributing to this scatter are examined, including the limited availability of some important constraining measurements, particularly CH3OOH. Some high concentrations of CH2O

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Ionic complexation of N 2O 4 by 18-crown-6

NASA Astrophysics Data System (ADS)

Ricard, S.; Audet, P.; Savoie, R.

1988-08-01

An ionic complex has been obtained from N 2O 4 in the presence of the macrocyclic ether 18-crown-6. This crystalline compound has been shown from its Raman spectrum to have the formula NO +·crown·H(NO 3) 2-, with the nitrosonium ion closely associated with the crown ether rather than with the hydrogen dinitrate accompanying ion. This adduct decomposes readily in moist air to give the known complex (HNO 3·H 2O) 2·crown.

Roles of free radicals in NO oxidation by Fenton system and the enhancement on NO oxidation and H2O2 utilization efficiency.

PubMed

Zhao, Haiqian; Dong, Ming; Wang, Zhonghua; Wang, Huaiyuan; Qi, Hanbing

2018-06-20

Low H 2 O 2 utilization efficiency is the main problem when Fenton system was used to oxidize NO in flue gas. To understand the behavior of the free radicals during NO oxidation process in Fenton system is crucial to solving this problem. The oxidation capacity of ·OH and HO 2 · on NO in Fenton system was compared and the useless consumption path of ·OH and HO 2 · that caused the low utilization efficiency of H 2 O 2 were studied. A method to enhance the oxidation ability and H 2 O 2 utilization efficiency by adding reducing additives in Fenton system was proposed. The results showed that both of ·OH and HO 2 · were active substances that oxidize NO. However, the oxidation ability of ·OH radicals was stronger. The vast majority of ·OH and HO 2 · was consumed by rapid reaction ·OH+HO 2 ·→H 2 O+O 2 , which was the primary reason for the low utilization efficiency of H 2 O 2 in Fenton system. Hydroxylamine hydrochloride and ascorbic acid could accelerate the conversion of Fe 3+ to Fe 2+ , thereby increase the generation rate of ·OH and decrease the generation rate of HO 2 ·. As a result, the oxidation ability and H 2 O 2 utilization efficiency were enhanced.

(Cu 0.5Tl 0.5)Ba 2Ca n-1 Cu n- yGe yO 2 n+4- δ ( n = 3, 4 and y = 0.5, 0.75, 1.0); superconductors with GeO 2 planes

NASA Astrophysics Data System (ADS)

Khan, Nawazish A.; Irfan, M.

2008-12-01

We have successfully synthesized germanium doped (Cu 0.5Tl 0.5)Ba 2Ca n-1 Cu n- yGe yO 2 n+4- δ ( n = 3, 4 and y = 0, 0.5, 0.75, 1.0) superconductors and investigated the effect of Ge doping on the superconducting properties of these compounds. The solubility of Ge till y = 1 in the CuO 2 planes of (Cu 0.5Tl 0.5)Ba 2Ca 2Cu 3- yGe yO 10- δ, have been found to give superconductivity above 77 K. To our surprise an enhanced superconductivity is observed with the doping of semiconductor germanium in some samples. The enhanced superconductivity associated with mixed CuO 2/GeO 2 planes can be extremely useful for the understanding of mechanism of superconductivity; since we very well know the properties of germanium based semiconductors.

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

Synthesis, crystal structure, and thermal behavior of the rare earth sulfates (H{sub 5}O{sub 2})M(SO{sub 4}){sub 2} (M = Ho, Er, Y)

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

Wickleder, M.S.

1998-10-01

The compounds (H{sub 5}O{sub 2})M(SO{sub 4}){sub 2} (M = Ho, Er, Y) were obtained from the metal oxides M{sub 2}O{sub 3} (M = Ho, Er,m Y) using diluted sulfuric acid (80%). The crystal structure of the isotypic compounds has been determined from single-crystal data by direct and Fourier methods. The characteristic feature of the crystal structure is a network of edge-sharing [MO{sub 8}] trigon dodecahedra and [SO{sub 4}] tetrahedra providing channels along [111] which are occupied by disordered H{sub 5}O{sub 2}{sup +} ions. In situ X-ray powder investigations exhibit that the compounds are also formed as intermediate phases during themore » reaction of the hydrogen sulfates M(HSO{sub 4}){sub 3} (M = Ho, Er, Y) with water. According to DSC measurements and temperature-dependent powder diffraction studies, the thermal decomposition of the title compounds follows a two-step mechanism. Around 150 C, two molecules of water are driven off, yielding M(HSO{sub 4})(SO{sub 4}) (M = Ho, Er, Y), and finally, at 320 C, H{sub 2}SO{sub 4} (H{sub 2}O + SO{sub 3}) is released to give the anhydrous sulfates M{sub 2}(SO{sub 4}){sub 3}.« less

Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

NASA Astrophysics Data System (ADS)

Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy­ethyl)methylamino]ethanolato-2:1κ4 O 1,N,O 2:O 1}[μ-2,2′-(methylimino)diethanolato-1:2κ4 O,N,O′:O]dithiocyanato-1κN,2κN-chromium(III)copper(II)

PubMed Central

Rusanova, Julia A.; Semenaka, Valentina V.; Dyakonenko, Viktoriya V.; Shishkin, Oleg V.

2015-01-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal CuII/CrIII complex. The mol­ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio­cyanato ligands. The CuII ion adopts a distorted square-pyramidal coordination while the CrIII ion has a distorted octa­hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O—H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two –CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1). PMID:26396853

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.

Crystal chemistry and the role of ionic radius in rare earth tetrasilicates: Ba2RE2Si4O12F2 (RE = Er3+-Lu3+) and Ba2RE2Si4O13 (RE = La3+-Ho3+).

PubMed

Fulle, Kyle; Sanjeewa, Liurukara D; McMillen, Colin D; Kolis, Joseph W

2017-10-01

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE 2 Si 4 O 12 F 2 (RE = Er 3+ -Lu 3+ ) and new compounds in the Ba 2 RE 2 Si 4 O 13 (RE = La 3+ -Ho 3+ ) family, covering the whole range of ionic radii for the rare earth ions. The Ba 2 RE 2 Si 4 O 13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\\overline 1} for La 3+ -Nd 3+ , and space group C2/c for Sm 3+ -Ho 3+ ). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

N2O, NO, N2 and CO2 emissions from tropical savanna and grassland of northern Australia: an incubation experiment with intact soil cores

NASA Astrophysics Data System (ADS)

Werner, C.; Reiser, K.; Dannenmann, M.; Hutley, L. B.; Jacobeit, J.; Butterbach-Bahl, K.

2014-11-01

Strong seasonal variability of hygric and thermal soil conditions are a defining environmental feature in northern Australia. However, how such changes affect the soil-atmosphere exchange of nitrous oxide (N2O), nitric oxide (NO) and dinitrogen (N2) is still not well explored. By incubating intact soil cores from four sites (three savanna, one pasture) under controlled soil temperatures (ST) and soil moisture (SM) we investigated the release of the trace gas fluxes of N2O, NO and carbon dioxide (CO2). Furthermore, the release of N2 due to denitrification was measured using the helium gas flow soil core technique. Under dry pre-incubation conditions NO and N2O emissions were very low (<7.0 ± 5.0 μg NO-N m-2 h-1; <0.0 ± 1.4 μg N2O-N m-2 h-1) or in the case of N2O, even a net soil uptake was observed. Substantial NO (max: 306.5 μg N m-2 h-1) and relatively small N2O pulse emissions (max: 5.8 ± 5.0 μg N m-2 h-1) were recorded following soil wetting, but these pulses were short lived, lasting only up to 3 days. The total atmospheric loss of nitrogen was generally dominated by N2 emissions (82.4-99.3% of total N lost), although NO emissions contributed almost 43.2% to the total atmospheric nitrogen loss at 50% SM and 30 °C ST incubation settings (the contribution of N2 at these soil conditions was only 53.2%). N2O emissions were systematically higher for 3 of 12 sample locations, which indicates substantial spatial variability at site level, but on average soils acted as weak N2O sources or even sinks. By using a conservative upscale approach we estimate total annual emissions from savanna soils to average 0.12 kg N ha-1 yr-1 (N2O), 0.68 kg N ha-1 yr-1 (NO) and 6.65 kg N ha-1 yr-1 (N2). The analysis of long-term SM and ST records makes it clear that extreme soil saturation that can lead to high N2O and N2 emissions only occurs a few days per year and thus has little impact on the annual total. The potential contribution of nitrogen released due to pulse events

{μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II).

PubMed

Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

2012-08-01

Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

Visible Light Assisted Photocatalytic Hydrogen Generation by Ta 2O 5/Bi 2O 3, TaON/Bi 2O 3, and Ta 3N 5/Bi 2O 3 Composites

DOE PAGES

Adhikari, Shiba; Hood, Zachary D.; More, Karren Leslie; ...

2015-06-15

Composites comprised of two semiconducting materials with suitable band gaps and band positions have been reported to be effective at enhancing photocatalytic activity in the visible light region of the electromagnetic spectrum. Here, we report the synthesis, complete structural and physical characterizations, and photocatalytic performance of a series of semiconducting oxide composites. UV light active tantalum oxide (Ta2O5) and visible light active tantalum oxynitride (TaON) and tantalum nitride (Ta 3N 5) were synthesized, and their composites with Bi 2O 3 were prepared in situ using benzyl alcohol as solvent. The composite prepared using equimolar amounts of Bi 2O 3 andmore » Ta 2O 5 leads to the formation of the ternary oxide, bismuth tantalate (BiTaO 4) upon calcination at 1000 °C. The composites and single phase bismuth tantalate formed were characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) surface area measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–Vis diffuse reflectance spectroscopy, and photoluminescence. The photocatalytic activities of the catalysts were evaluated for generation of hydrogen using aqueous methanol solution under visible light irradiation (λ ≥ 420 nm). The results show that as-prepared composite photocatalysts extend the light absorption range and restrict photogenerated charge-carrier recombination, resulting in enhanced photocatalytic activity compared to individual phases. The mechanism for the enhanced photocatalytic activity for the heterostructured composites is elucidated based on observed activity, band positions calculations, and photoluminescence data.« less

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

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

Lai, Jun-Kun; Wachs, Israel E.

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

DOE PAGES

Lai, Jun-Kun; Wachs, Israel E.

2018-06-04

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

Poly[[aqua­(μ2-oxalato)(μ2-2-oxido­pyridinium-3-carboxylato)holmium(III)] monohydrate

PubMed Central

Zhu, Hui-Lan; Lai, Hui-Ling; Han, Lu; Luo, Yi-Fan; Zeng, Rong-Hua

2009-01-01

In the title complex, {[Ho(C2O4)(C6H4NO3)(H2O)]·(H2O)}n, the HoIII ion is coordinated by three O atoms from two 2-oxidopyridinium-3-carboxylate ligands, four O atoms from two oxalate ligands and one water mol­ecule in a distorted bicapped trigonal-prismatic geometry. The 2-oxidopyridin­ium-3-carboxylate and oxalate ligands link the HoIII ions into a layer in (100). These layers are further connected by inter­molecular O—H⋯O hydrogen bonds involving the coordinated water mol­ecules to assemble a three-dimensional supra­molecular network. The uncoordin­ated water mol­ecule is involved in N—H⋯O and O—H⋯O hydrogen bonds within the layer. PMID:21577741

Volume properties and refraction of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids lysine, threonine, and oxyproline (C60(C6H13N2O2)2, C60(C4H8NO3)2, and C60(C5H9NO2)2) at 25°C

NASA Astrophysics Data System (ADS)

Semenov, K. N.; Ivanova, N. M.; Charykov, N. A.; Keskinov, V. A.; Kalacheva, S. S.; Duryagina, N. N.; Garamova, P. V.; Kulenova, N. A.; Nabieva, A.

2017-02-01

Concentration dependences of the density of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids are studied by pycnometry. Concentration dependences of the average molar volumes and partial volumes of components (H2O and corresponding bisadducts) are calculated for C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems at 25°C. Concentration dependences of the indices of refraction of C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems are determined at 25°C. The concentration dependences of specific refraction and molar refraction of bisadducts and aqueous solutions of them are calculated.

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

DOE PAGES

Zhao, Z. Y.; Calder, S.; Aczel, A. A.; ...

2016-04-25

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Fragile singlet ground-state magnetism in the pyrochlore osmates R 2 Os 2 O 7 ( R = Y and Ho)

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

Zhao, Z. Y.; Calder, S.; Aczel, A. A.

The singlet ground state magnetism in pyrochlore osmates Y 2Os 2O 7 and Ho 2Os 2O 7 is studied by DC and AC susceptibility, specific heat, and neutron powder diffraction measurements. Despite the expected non-magnetic singlet in the strong spin-orbit coupling (SOC) limit for Os 4+ (5d 4), Y 2Os 2O 7 exhibits a spin-glass (SG) ground state below 4 K with weak magnetism, suggesting possible proximity to a quantum phase transition between the non-magnetic state in the strong SOC limit and the magnetic state in the strong superexchange limit. Ho 2Os 2O 7 has the same structural distortion asmore » occurs in Y 2Os 2O 7. However, the Os sublattice in Ho 2Os 2O 7 shows long- range magnetic ordering below 36 K. We find that the sharp difference of the magnetic ground state between Y 2Os 2O 7 and Ho 2Os 2O 7 signals the singlet ground state magnetism in R 2 Os 2 O 7 is fragile and can be disturbed by the weak 4f—5d interactions.« less

Bis(2,3,5,6-tetra-2-pyridylpyrazine-κ3 N 2,N 1,N 6)iron(II) bis­(dicyanamidate) 4.5-hydrate

PubMed Central

Callejo, L.; De la Pinta, N.; Madariaga, G.; Fidalgo, M.L.; Cortés, R.

2010-01-01

In the title compound, [Fe(C24H16N6)2][N(CN)2]2·4.5H2O, the central iron(II) ion is hexa­coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz) ligands. Two dicyanamide anions [dca or N(CN)2 −] act as counter-ions, and 4.5 water mol­ecules act as solvation agents. The structure contains isolated cationic iron(II)–tppz complexes and the final neutrality is obtained with the two dicyanamide anions. One of the dicyanamide anions and a water mol­ecule are disordered with an occupancy ratio of 0.614 (8):0.386 (8). O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds involving dca, water and tppz mol­ecules are observed. PMID:21580205

Double Q-switch Ho:Sc2SiO5 laser by acousto-optic modulator combined with Cr2+:ZnSe saturable absorber

NASA Astrophysics Data System (ADS)

Yang, Xiao-tao; Zhang, Peng; Xie, Wen-qiang; Li, Lin-jun

2018-01-01

A double Q-switch (DQS) Ho:Sc2SiO5 laser modulated by a acousto-optic modulators (AOM) combined with a Cr2+:ZnSe saturable absorber (SA) was reported for the first time. The actively Q-switch (AQS) and passively Q-switch (PQS) were also studied. For the DQS mode, a maximum average output power of 2.49 W under the incident pump power of 12.5 W was obtained, corresponding to a slope efficiency of 24%. The characteristics of the DQS Ho:SSO laser versus different repetition frequencies (RF) of the AOM were researched. The maximum single-pulse energy of the DQS Ho:SSO laser was calculated to 1.98 mJ. The maximum peak power of the DQS Ho:SSO laser was 49.5 kW. The output beam quality factor M2 of DQS Ho:SSO laser was measured to be 1.15 with the highest peak power by knife-edge method at different positions.

Observed NO/NO2 Ratios in the Upper Troposphere Imply Errors in NO-NO2-O3 Cycling Kinetics or an Unaccounted NOx Reservoir

NASA Astrophysics Data System (ADS)

Silvern, R. F.; Jacob, D. J.; Travis, K. R.; Sherwen, T.; Evans, M. J.; Cohen, R. C.; Laughner, J. L.; Hall, S. R.; Ullmann, K.; Crounse, J. D.; Wennberg, P. O.; Peischl, J.; Pollack, I. B.

2018-05-01

Observations from the SEAC4RS aircraft campaign over the southeast United States in August-September 2013 show NO/NO2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NOx reservoir species, presumably organic, decomposing thermally to NO2 in the instrument. The NO2 instrument corrects for this artifact from known labile HNO4 and CH3O2NO2 NOx reservoirs. To bridge the gap between measured and simulated NO2, additional unaccounted labile NOx reservoir species would have to be present at a mean concentration of 40 ppt for the SEAC4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low-temperature rate constant for the NO + O3 reaction (30% 1-σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO2 photolysis (20% 1-σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO2 columns.

Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

2017-09-01

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-12-14

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N and O isotope (δ15 Nα , δ15 Nβ , δ18 O, δ17 O) analyses of dissolved NO3- and NO2- by the Cd-azide reduction method and N2 O laser spectrometry.

PubMed

Wassenaar, Leonard I; Douence, Cedric; Altabet, Mark A; Aggarwal, Pradeep K

2018-02-15

The nitrogen and oxygen (δ 15 N, δ 18 O, δ 17 O) isotopic compositions of NO 3 - and NO 2 - are important tracers of nutrient dynamics in soil, rain, groundwater and oceans. The Cd-azide method was used to convert NO 3 - or NO 2 - to N 2 O for N and triple-O isotopic analyses by N 2 O laser spectrometry. A protocol for laser-based headspace isotope analyses was compared with isotope ratio mass spectrometry. Lasers provide the ability to directly measure 17 O anomalies which can help discern atmospheric N sources. δ 15 N, δ 18 O and δ 17 O values were measured on N/O stable isotopic reference materials (IAEA, USGS) by conversion to N 2 O using the Cd-azide method and headspace N 2 O laser spectrometry. A 15 N tracer test assessed the position-specific routing of N to the α or β positions in the N 2 O molecule. A data processing algorithm was used to correct for isotopic dependencies on N 2 O concentration, cavity pressure and water content. NO 3 - /NO 2 - nitrogen is routed to the 15 N α position of N 2 O in the azide reaction; hence the δ 15 N α value should be used for N 2 O laser spectrometry results. With corrections for cavity pressure, N 2 O concentration and water content, the δ 15 N α AIR , δ 18 O VSMOW and δ 17 O VSMOW values (‰) of international reference materials were +4.8 ± 0.1, +25.9 ± 0.3, +12.7 ± 0.2 (IAEA NO 3 ), -1.7 ± 0.1, -26.8 ± 0.8, -14.4 ± 1.1 (USGS34) and +2.6 ± 0.1, +57.6 ± 1.2, +51.2 ± 2.0 (USGS35), in agreement with their values and with the isotope ratio mass spectrometry results. The 17 O excess for USGS35 was +21.2 ± 9‰, in good agreement with previous results. The Cd-azide method yielded excellent results for routine determination of δ 15 N, δ 18 O and δ 17 O values (and the 17 O excess) of nitrate or nitrite by laser spectrometry. Disadvantages are the toxicity of Cd-azide chemicals and the lack of automated sampling devices for N 2 O laser spectrometers. The 15 N-enriched tracer test revealed potential

Is the 'Bromine Explosion' generated from the reaction BrO HO2 alone?

NASA Astrophysics Data System (ADS)

Behnke, Wolfgang; Zetzsch, Cornelius

2010-05-01

We observed bromine explosions (a fast production of atomic Br and Cl under tropospheric conditions) in various smog chamber experiments in Teflon bags at room temperature at a relative humidity of about 80% in the presence of NaCl/NaBr-aerosol, simulated sunlight and ozone (200 - 400 ppb). Time profiles of ozone and hydrocarbons (HCs: n-butane, 2,2-dimethylbutane, tetramethylbutane and toluene, initially about 2 ppb each) were monitored to determine concentrations and source strengths of OH radicals, atomic Cl and Br and the corresponding time profiles of BrCl and Br2 as their photolytic precursors. The number and size of aerosols are measured as well as their chemical composition (Br-, Cl- and oxalic acid). Full records of raw data from the smog chamber runs are available at www.eurochamp.org for potential users. Chemical box model calculations deliver concentrations of various intermediates, such as aldehydes, HO2 and RO2 radicals and the inorganic halogen compounds ClO, BrO, HOCl and HOBr, where HOBr from O3 + Br- => BrO- + O2 in the aqueous/adsorbed phase induces the following gas-phase/ heterogeneous chain reaction Br + O3 => BrO + O2(1) BrO + HO2 => HOBr + O2(2a) HOBr + (Aerosol) => HOBrad(3) Surface-adsorbed HOBr reacts with Br- or Cl- to produce Br2 or BrCl, both of which are released and photolysed. Formation of Br2 should prevail up to Cl-/Br- -ratios of about 104 (Fickert, S., J.W. Adams, J.N. Crowley, J. Geophys. Res., D104, 23719-23727, 1999). A maximum of this ratio is reached about 30 minutes after the beginning and decreases during the next hours - probably by reaction of Br2 with oxalate and absorption of HBr, formed from the reaction of Br with aldehydes. Parallel to chain reaction (1)-(3) a chain reaction replacing Br by Cl seems possible but can not be realized, since the main sink of atomic Cl is its reaction with hydrocarbons - leading to chain termination - in contrast to atomic Br (ratio of rates: kCl[O3]/kCl[HC] ~ 0.1; kBr[O3]/k

Vertical profiles in NO3 and N2O5 measured from an aircraft: Results from the NOAA P-3 and surface platforms during the New England Air Quality Study 2004

NASA Astrophysics Data System (ADS)

Brown, Steven S.; Dubé, William P.; Osthoff, Hans D.; Stutz, Jochen; Ryerson, Thomas B.; Wollny, Adam G.; Brock, Charles A.; Warneke, Carsten; de Gouw, Joost A.; Atlas, Eliot; Neuman, J. Andrew; Holloway, John S.; Lerner, Brian M.; Williams, Eric J.; Kuster, William C.; Goldan, Paul D.; Angevine, Wayne M.; Trainer, Michael; Fehsenfeld, Frederick C.; Ravishankara, A. R.

2007-11-01

The nocturnal nitrogen oxides, NO3 and N2O5, are important to the chemical transformation and transport of NOx, O3 and VOC. Their concentrations, sources and sinks are known to be vertically stratified in the nighttime atmosphere. In this paper, we report vertical profiles for NO3 and N2O5 measured from an aircraft (the NOAA P-3) as part of the New England Air Quality Study in July and August 2004. The aircraft data are compared to surface measurements made in situ from a ship and by long-path DOAS. Consistent with previous, vertically resolved studies of NO3 and N2O5, the aircraft measurements show that these species occur at larger concentrations and are longer lived aloft than they are at the surface. The array of in situ measurements available on the P-3 allows for investigation of the mechanisms that give rise to the observed vertical gradients. Selected vertical profiles from this campaign illustrate the role of biogenic VOC, particularly isoprene and dimethyl sulfide, both within and above the nocturnal and/or marine boundary layer. Gradients in relative humidity and aerosol surface may also create a vertical gradient in the rate of N2O5 hydrolysis. Low-altitude intercepts of power plant plumes showed strong vertical stratification, with plume depths of 80 m. The efficiency of N2O5 hydrolysis within these plumes was an important factor determining the low-level NOx and O3 transport or loss at night. Averages of nocturnal O3, NO2, NO3 and N2O5 binned according to altitude were consistent with the trends from individual profiles. While production rates of NO3 peaked near the surface, lifetimes of NO3 and N2O5 were maximum aloft, particularly in the free troposphere. Variability in NO3 and N2O5 was large and exceeded that of NO2 or O3 because of inhomogeneous distribution of NOx emissions and NO3 and N2O5 sinks.

TES/Aura L2 Ozone (O3) Nadir V6 (TL2O3N)

Atmospheric Science Data Center

2018-01-18

TES/Aura L2 Ozone (O3) Nadir (TL2O3N) News:  TES News Join ... Project Title:  TES Discipline:  Tropospheric Composition Version:  V6 Level:  L2 Platform:  TES/Aura L2 Ozone Spatial Coverage:  5.3 x 8.5 km nadir ...

HNO and NO release from a primary amine-based diazeniumdiolate as a function of pH

PubMed Central

Salmon, Debra J.; Torres de Holding, Claudia L.; Thomas, Lynta; Peterson, Kyle V.; Goodman, Gens P.; Saavedra, Joseph E.; Srinivasan, Aloka; Davies, Keith M.; Keefer, Larry K.; Miranda, Katrina M.

2011-01-01

The growing evidence that nitroxyl (HNO) has a rich pharmacological potential that differs from that of nitric oxide (NO) has intensified interest in HNO donors. Recently, the diazeniumdiolate (NONOate) based on isopropylamine (IPA/NO; Na[(CH3)2CHNH(N(O)NO)]) was demonstrated to function under physiological conditions as an organic analogue to the commonly used HNO donor Angeli’s salt (Na2N2O3). The decomposition mechanism of Angeli’s salt is dependent on pH, with transition from an HNO to an NO donor occurring abruptly near pH 3. Here, pH is shown to also affect product formation from IPA/NO. Chemical analysis of HNO and NO production led to refinement of an earlier, quantum mechanically based prediction of the pH-dependent decomposition mechanisms of primary amine NONOates such as IPA/NO. Under basic conditions, the amine proton of IPA/NO is able to initiate decomposition to HNO by tautomerization to the nitroso nitrogen (N2). At lower pH, protonation activates a competing pathway to NO production. At pH 8, the donor properties of IPA/NO and Angeli’s salt are demonstrated to be comparable, suggesting that at or above this pH, IPA/NO is primarily an HNO donor. Below pH 5, NO is the major product, while IPA/NO functions as a dual donor of HNO and NO at intermediate pH. This pH-dependent variability in product formation may prove useful in examination of the chemistry of NO and HNO. Furthermore, primary amine NONOates may serve as a tunable class of nitrogen oxide donor. PMID:21405089

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