共查询到20条相似文献，搜索用时 15 毫秒
1.
Talukdar R Mellouki A Gierczak T Burkholder JB McKeen SA Ravishankara AR 《Science (New York, N.Y.)》1991,252(5006):693-695
The rate coefficients, k(1), for the reaction of OH with CHF(2)Br have been measured using pulsed photolysis and discharge flow techniques at temperatures (T) between 233 and 432 K to be k(1), = (7.4 +/- 1.6) x 10(-13) exp[-(1300 +/- 100)/T] cubic centimeters per molecule per second. The ultraviolet absorption cross sections, sigma, of this molecule between 190 and 280 nanometers were measured at 296 K. The k(1), and sigma values were used in a one-dimensional model to obtain an atmospheric lifetime of approximately 7 years for CHF(2)Br. This lifetime is shorter by approximately factors of 10 and 2 than those for CF(3)Br and CF(2)ClBr, respectively. The ozone depletion potentials of the three compounds will reflect these lifetimes. 相似文献
2.
Near ambient pressures, molecular diffusion dominates protonic diffusion in ice. Theoretical studies have predicted that protonic diffusion will dominate at high pressures in ice. We measured the protonic diffusion coefficient for the highest temperature molecular phase of ice VII at 400 kelvin over its entire stable pressure region. The values ranged from 10(-17) to 10(-15) square meters per second at pressures of 10 to 63 gigapascals. The diffusion coefficients extrapolated to high temperatures close to the ice VII melting curve were less by a factor of 10(2) to 10(3) than a superionic criterion of approximately 10(-8) square meters per second, at which protons would diffuse freely. 相似文献
3.
Berndt T Böge O Stratmann F Heintzenberg J Kulmala M 《Science (New York, N.Y.)》2005,307(5710):698-700
We investigated the formation of new particles in a laboratory study, starting from H2SO4 produced in situ through the reaction of OH radicals with SO2. Newly formed particles were observed for H2SO4 concentrations above 7 x 10(6) per cubic centimeter. At 293 kelvin, a rough estimate yielded a nucleation rate of 0.3 to 0.4 particles per cubic centimeter per second for approximately 10(7) particles per cubic centimeter of H2SO4 (particle size >/= 3 nanometers). These findings are in agreement with observations from the atmosphere. The results demonstrate that under laboratory conditions similar to the atmosphere, particle formation occurs at atmospheric H2SO4 concentration levels. 相似文献
4.
Prinn RG Weiss RF Miller BR Huang J Alyea FN Cunnold DM Fraser PJ Hartley DE Simmonds PG 《Science (New York, N.Y.)》1995,269(5221):187-192
Determination of the atmospheric concentrations and lifetime of trichloroethane (CH(3)CCI(3)) is very important in the context of global change. This halocarbon is involved in depletion of ozone, and the hydroxyl radical (OH) concentrations determined from its lifetime provide estimates of the lifetimes of most other hydrogen-containing gases involved in the ozone layer and climate. Global measurements of trichloroethane indicate rising concentrations before and declining concentrations after late 1991. The lifetime of CH(3)CCI(3) in the total atmosphere is 4.8 +/- 0.3 years, which is substantially lower than previously estimated. The deduced hydroxyl radical concentration, which measures the atmosphere's oxidizing capability, shows little change from 1978 to 1994. 相似文献
5.
Asvany O P PK Redlich B Hegemann I Schlemmer S Marx D 《Science (New York, N.Y.)》2005,309(5738):1219-1222
Protonated methane, CH5+, continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH5+ is presented, as detected by reaction with carbon dioxide gas after resonant excitation by the free electron laser at the FELIX facility in the Netherlands. Comparison of the experimental spectrum at approximately 110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH5+ under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH3 tripod positions and the three-center bonded H2 moiety, which eventually leads to full hydrogen scrambling. The possibility of artificially freezing out scrambling and internal rotation in the simulations allowed assignment of the infrared spectrum despite this pronounced fluxionality. 相似文献
6.
The elusive protonated ozone ion (O(3)H(+)) has been long postulated as a reactive intermediate but never experimentally observed. This ion has been detected here in mass spectrometric experiments with the use of Fourier transform ion cyclotron resonance. In these experiments, ozone (O(3)) was protonated by strong acids-for example, H(3)(+), KrH(+), XeH(+), and CH(5)(+). The hitherto experimentally unknown proton affinity of O(3) was evaluated by a "bracketing" technique and determined to be 148 -/+ 3 kilocalories mole(-1) at 298 kelvin, in excellent agreement with a value determined in a recent theoretical study of the O(3)/O(3)H(+) system, which was 148 kilocalories mole(-1) at zero temperature ( approximately 149.5 kilocalories mole(-1) at 298 kelvin). 相似文献
7.
Manriquez JM Yee GT McLean RS Epstein AJ Miller JS 《Science (New York, N.Y.)》1991,252(5011):1415-1417
The reaction of bis(benzene)vanadium with tetracyanoethylene, TCNE, affords an insoluble amorphous black solid that exhibits field-dependent magnetization and hysteresis at room temperature. The critical temperature could not be estimated as it exceeds 350 kelvin, the thermal decomposition temperature of the sample. The empirical composition of the reported material is V(TCNE)x.Y(CH(2)Cl(2)) with x approximately 2 and Y approximately 1/2. On the basis of the available magnetic and infrared data, threedimensional antiferromagnetic exchange of the donor and acceptor spins resulting in ferrimagnetic behavior appears to be the mode of magnetic coupling. 相似文献
8.
Chemical dynamics trajectory simulations were used to study the atomic-level mechanisms of the OH- + CH3F --> CH3OH + F- SN2 nucleophilic substitution reaction. The reaction dynamics, from the [OH...CH3...F]- central barrier to the reaction products, are simulated by ab initio direct dynamics. The reaction's potential energy surface has a deep minimum in the product exit channel arising from the CH3OH...F- hydrogen-bonded complex. Statistical theories of unimolecular reaction rates assume that the reactive system becomes trapped in this minimum and forms an intermediate, with random redistribution of its vibrational energy, but the majority of the trajectories (90%) avoided this potential energy minimum and instead dissociated directly to products. This finding is discussed in terms of intramolecular vibrational energy redistribution (IVR) and the relation between IVR and molecular structure. The finding of this study may be applicable to other reactive systems where there is a hierarchy of time scales for intramolecular motions and thus inefficient IVR. 相似文献
9.
The measured reaction probability, gamma for the reaction of chlorine nitrate (CIONa(2)) with 60 percent (by weight) sulfuric acid aerosol increases monotonically with particle size at 250 kelvin. The reacto-diffusive length (l, the effective liquid depth over which reaction occurs) derived from these experiments is 0.037 +/- 0.007 micrometer (95 percent confidence level for precision). The reaction probability for the reaction of CIONO(2) with 60 percent sulfuric acid aerosol doped with approximately 7 x 10(-4) M hydrochloric acid at 250 kelvin is larger by about a factor of 4 than in the absence of hydrochloric acid and varies less with particle size (l = 0.009 +/- 0.005 micrometer). These results provide a test of the theory for gas-particle reactions and further insight into the reactivity of atmospheric aerosol. 相似文献
10.
Meibom A Desch SJ Krot AN Cuzzi JN Petaev MI Wilson L Keil K 《Science (New York, N.Y.)》2000,288(5467):839-841
Chemical zoning patterns in some iron, nickel metal grains from CH carbonaceous chondrites imply formation at temperatures from 1370 to 1270 kelvin by condensation from a solar nebular gas cooling at a rate of approximately 0.2 kelvin per hour. This cooling rate requires a large-scale thermal event in the nebula, in contrast to the localized, transient heating events inferred for chondrule formation. In our model, mass accretion through the protoplanetary disk caused large-scale evaporation of precursor dust near its midplane inside of a few astronomical units. Gas convectively moved from the midplane to cooler regions above it, and the metal grains condensed in these parcels of rising gas. 相似文献
11.
Nuñez-Regueiro M Tholence JL Antipov EV Capponi JJ Marezio M 《Science (New York, N.Y.)》1993,262(5130):97-99
The recently discovered homologous series HgBa(2)Can-1 Cun O2n+2+delta possesses remarkable properties. A superconducting transition temperature, T(c), as high as 133 kelvin has been measured in a multiphase Hg-Ba-Ca-Cu-O sample and found to be attributable to the Hg-1223 compound. Temperature-dependent electrical resistivity measurements under pressure on a (> 95%) pure Hg-1223 phase are reported. These data show that T(c) increases steadily with pressure at a rate of about 1 kelvin per gigapascal up to 15 gigapascals, then more slowly and reaches a T(c) = 150 kelvin, with the onset of the transition at 157 kelvin, for 23.5 gigapascals. This large pressure variation (as compared to the small effects observed in similar compounds with the optimal T(c)) strongly suggests that higher critical temperatures could be obtained at atmospheric pressure. 相似文献
12.
Films of silicon dioxide (SiO2) were deposited at room temperature by means of catalyzed binary reaction sequence chemistry. The binary reaction SiCl4 + 2H2O --> SiO2 + 4HCl was separated into SiCl4 and H2O half-reactions, and the half-reactions were then performed in an ABAB ellipsis sequence and catalyzed with pyridine. The pyridine catalyst lowered the deposition temperature from >600 to 300 kelvin and reduced the reactant flux required for complete reactions from approximately 10(9) to approximately 10(4) Langmuirs. Growth rates of approximately 2.1 angstroms per AB reaction cycle were obtained at room temperature for reactant pressures of 15 millitorr and 60-second exposure times with 200 millitorr of pyridine. This catalytic technique may be general and should facilitate the chemical vapor deposition of other oxide and nitride materials. 相似文献
13.
Zhong D Franke JH Podiyanachari SK Blömker T Zhang H Kehr G Erker G Fuchs H Chi L 《Science (New York, N.Y.)》2011,334(6053):213-216
In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation. 相似文献
14.
The trapping-mediated dissociative chemisorption of three isotopes of propane (C(3)H(8), CH(3),CD(2)CH(3), and C(3)D(8)) has been investigated on the Pt(110)-(1 x 2) surface, and both the apparent activation energies and the preexponential factors of the surface reaction rate coefficients have been measured. In addition, the probabilities of primary and secondary C-H bond cleavage for alkane activation on a surface were evaluated. The activation energy for primary C-H bond cleavage was 425 calories per mole greater than that of secondary C-H bond cleavage, and the two true activation energies that embody the single measured activation energy were determined for each of the three isotopes. Secondary C-H bond cleavage is also preferred on entropic grounds, and the magnitude of the effect was quantified. 相似文献
15.
Welz O Savee JD Osborn DL Vasu SS Percival CJ Shallcross DE Taatjes CA 《Science (New York, N.Y.)》2012,335(6065):204-207
Ozonolysis is a major tropospheric removal mechanism for unsaturated hydrocarbons and proceeds via "Criegee intermediates"--carbonyl oxides--that play a key role in tropospheric oxidation models. However, until recently no gas-phase Criegee intermediate had been observed, and indirect determinations of their reaction kinetics gave derived rate coefficients spanning orders of magnitude. Here, we report direct photoionization mass spectrometric detection of formaldehyde oxide (CH(2)OO) as a product of the reaction of CH(2)I with O(2). This reaction enabled direct laboratory determinations of CH(2)OO kinetics. Upper limits were extracted for reaction rate coefficients with NO and H(2)O. The CH(2)OO reactions with SO(2) and NO(2) proved unexpectedly rapid and imply a substantially greater role of carbonyl oxides in models of tropospheric sulfate and nitrate chemistry than previously assumed. 相似文献
16.
PO Wennberg TF Hanisco L Jaegle DJ Jacob EJ Hintsa EJ Lanzendorf JG Anderson R Gao ER Keim SG Donnelly LAD Negro DW Fahey SA McKeen RJ Salawitch CR Webster RD May RL Herman MH Proffitt JJ Margitan EL Atlas SM Schauffler F Flocke CT McElroy TP Bui 《Science (New York, N.Y.)》1998,279(5347):49-53
The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected. 相似文献
17.
Prinn RG Huang J Weiss RF Cunnold DM Fraser PJ Simmonds PG McCulloch A Harth C Salameh P O'Doherty S Wang RH Porter L Miller BR 《Science (New York, N.Y.)》2001,292(5523):1882-1888
The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself. 相似文献
18.
Real JA Andrés E Muñoz MC Julve M Granier T Bousseksou A Varret F 《Science (New York, N.Y.)》1995,268(5208):265-267
The compound [Fe(tvp)(2)(NCS)(2)] . CH(3)OH, where tvp is 1,2-di-(4-pyridyl)-ethylene, has been synthesized and characterized by x-ray single-crystal diffraction. It consists of two perpendicular, two-dimensional networks organized in parallel stacks of sheets made up of edge-shared [Fe(II)](4) rhombuses. The fully interlocked networks define large square channels in the [001] direction. Variable-temperature magnetic susceptibility measurements and M?ssbauer studies reveal that this compound shows low-spin to high-spin crossover behavior in the temperature range from 100 to 250 kelvin. The combined structural and magnetic characterization of this kind of compound is fundamental for the interpretation of the mechanism leading to the spin crossover, which is important in the development of electronic devices such as molecular switches. 相似文献
19.
How much more rain will global warming bring? 总被引：2，自引：0，他引：2
Climate models and satellite observations both indicate that the total amount of water in the atmosphere will increase at a rate of 7% per kelvin of surface warming. However, the climate models predict that global precipitation will increase at a much slower rate of 1 to 3% per kelvin. A recent analysis of satellite observations does not support this prediction of a muted response of precipitation to global warming. Rather, the observations suggest that precipitation and total atmospheric water have increased at about the same rate over the past two decades. 相似文献
20.
Sundström G Mowat JR Danared H Datz S Broström L Filevich A Källberg A Mannervik S Rensfelt KG Sigray P Ugglas MA Larsson M 《Science (New York, N.Y.)》1994,263(5148):785-787
Knowledge of the abundance of H(3)(+) is needed in interstellar and planetary atmospheric chemistry. An important destruction mechanism of H(3)(+) is low-energy electron impact followed by dissociation, but estimates of the reaction rate span several orders of magnitude. As an attempt to resolve this uncertainty, the cross section for dissociative recombination of vibrationally cold H(3)(+) has been measured with an ion storage ring down to collision energies below 1 millielectron volt. A rate coefficient of 1.15 x 10(-7) cubic centimeters per second at 300 kelvin was deduced. The cross section scaled with collision energy according to E(-1.15), giving thee rate a temperature dependence of T(-0.65). 相似文献