Nitric oxide reduction coupled with carbon monoxide oxidation in the presence of soluble metal catalysts

Solutions of RhCl(3).xH(2)O in ethanol and Ru(NO)(2)[P(C(6)H(5))(3)](2) in benzene catalyze the reduction of nitric oxide to nitrous oxide concomitant with the oxidation of carbon monoxide to carbon dioxide at ambient temperature and atmospheric pressure. The reaction, which is followed by gas chromatography and by the decrease in pressure of the system, proceeds to 47 percent conversion of the reactants after 63 hours.     

Doubly ionized carbon observed in the plasma tail of comet Kudo-Fujikawa

Comet C/2002 X5 (Kudo-Fujikawa) was observed near its perihelion of 0.19 astronomical unit by the Ultraviolet Coronagraph Spectrometer aboard the Solar and Heliospheric Observatory spacecraft. Images of the comet reconstructed from high-resolution spectra reveal a quasi-spherical cloud of neutral hydrogen and a variable tail of C+ and C2+ that disconnects from the comet and subsequently regenerates. The high abundance of C2+ and C+, at least 24% relative to water, cannot be explained by photodissociation of carbon monoxide and is instead attributed to the evaporation and subsequent photoionization of atomic carbon from organic refractory compounds present in the cometary dust grains. This result serves to strengthen the connection between comets and the material from which the Solar System formed.     

Apollo lunar module engine exhaust products

Organic combustion products generated by the lunar module descent engine, which burns a 1:1 mixture of unsymmetrical dimethylhydrazine fuel and nitrogen tetroxide oxidizer, have been analyzed. The major gaseous combustion products found were ammonia, water, carbon monoxide, nitrous oxide, oxygen, carbon dioxide, and nitric oxide. The minor products were acetylene, hydrogen cyanide, ethylene, formaldehyde, propadiene, ketene, cyanous acid, hydrazoic acid, various methylamines, acetaldehyde, methyl nitrite, formic acid, nitrous acid, butadiyne, nitrilohydrazines, nitromethane, and nitrosohydrazines with other oxidized derivatives of unsymmetrical dimethylhydrazine and hydrazine. The ion intensities of the various species in all mass spectra were estimated as the following concentrations: the gases (NH(3), H(2)O, CO, NO, O(2), CO(2), and NO(2)), 87.7 percent; compounds of C, H, and O, 6.0 percent; and compounds of C, H, and N (with traces of O), 5.8 percent.     

Titan: discovery of carbon monoxide in its atmosphere

The 3-0 rotation-vibration band of carbon monoxide in the near-infrared spectrum of Titan has been identified, and a reflecting layer model mixing ratio of carbon monoxide to molecular nitrogen of 6 x 10(-5) has been determined. This result supports the probable detection of carbon dioxide by Samuelson and his co-workers and strengthens possible analogies between the atmosphere of Titan and conditions on primitive Earth.     

Metal oxide chemistry in solution: the early transition metal polyoxoanions

Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces.     

Production of syngas by direct catalytic oxidation of methane

The reaction between methane and oxygen over platinum and rhodium surfaces in metalcoated ceramic monoliths can be made to produce mostly hydrogen and carbon monoxide (greater than 90% selectivity for both) with almost complete conversion of methane and oxygen at reaction times as short as 10(-3) seconds. This process has great promise for conversion of abundant natural gas into liquid products such as methanol and hydrocarbons, which can be easily transported from remote locations. Rhodium was considerably superior to platinum in producing more H(2) and less H(2)O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces.     

Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.     

Ammonioborite: new borate polyion and its structure

The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).     

Soil as a sink for atmospheric carbon monoxide

The rate of carbon monoxide oxidation by soil increased with increasing carbon monoxide concentration in the gas phase, in line with Michaelis-Menten kinetics. Rates of carbon monoxide oxidation were determined for 20 soils at 0 degrees , 10 degrees , 20 degrees , and 30 degrees C. The observed oxidation rates were used to calculate a global soil uptake rate of atmospheric carbon monoxide of 4.1 x 10(14) grams per year, which is slightly less than the amount of carbon monoxide believed to be produced annually as a result of fossil fuel combustion.     

Microwave measurements of carbon monoxide on titan

The ratio of the flux density of Titan was measured in two 200-megahertz bands, one centered on the (1-0) rotation line of carbon monoxide at 115.3 gigahertz and the other 2600 megahertz lower. The measurements were made with a complex-correlation technique on the new millimeter-wavelength interferometer at the Owens Valley Radio Observatory, Big Pine, California. The excess flux in the carbon monoxide band is interpreted as a strong detection of carbon monoxide and a mixing ratio, assumed constant, of 6 x 10(-5). The brightness temperature of Titan at 112.6 gigahertz is 69 +/- 10 kelvins, consistent with atmospheric emission from just below the tropopause.     

Water and carbon in rusty lunar rock 66095

Lunar rock 66095 contains a hydrated iron oxide and has an unusual amount of water for a lunar rock (140 to 750 parts per million), 90 percent of which is released below 690 degrees C. The deltaof water released at these low temperatures varies from -75 to -140 per mil relative to standard mean ocean water (SMOW). The small amount of water released between 690 degrees and 1300 degrees C has a delta of about -175 +/-25 per mil SMOW. These delta values are not unusual for terrestrial water. The delta(18)O of water extracted from 110 degrees to 400 degrees C has a value of +5+/- I per mil SMOW, similar to the value for lunar silicates from rock 66095 and different from the value of -4 to -22 per mil found for samples of terrestrial rust including samples of rusted meteoritic iron. The amount of carbon varies from 11 to 59 parts per million with a delta(13)C from -20 to -30 per mil relative to Pee Dee belemnite. Only very small amounts of reduced species (such as hydrogen, carbon monoxide, and methane) were found, in contrast to the analyses of other lunar rocks. Although it is possible that most of the water in the iron oxide (goethite) may be terrestrial in origin or may have exchanged with terrestrial water during sample return and handling, evidence presented herein suggests that this did not happen and that some lunar water may have a deltaD that is indistinguishable from that of terrestrial water.     

CH3·与CO反应机理的理论研究

采用密度泛函B3LYP/6-311G**和QC ISD(T)/6-311G**方法计算研究了CH3.与CO反应机理,全参数优化了反应势能面上各驻点的几何构型,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。研究结果表明:CO对CH3.自由基有稳定化作用。该反应的研究将为烃类的燃烧和大气环境的保护提供理论依据。     

Soil: a natural sink for carbon monoxide

A potting soil mixture depleted carbon monoxide in a test atmosphere from a concentration of 120 parts per million to near zero within 3 hours. Maximum activity occurred at 30 degrees C. Steam sterilization of the soil, the addition of antibiotics or 10 percent (by weight) saline solution, and anaerobic conditions all prevented carbon monoxide uptake. Sterilized soil inoculated with nonsterile soil acquired activity with time. Samples of various natural soils differed in their ability to remove carbon monoxide from the air. Acidic soils with a high content of organic matter were generally the most active. The soil's ability to remove carbon monoxide from the atmosphere is ascribed to the activity of soil micro-organisms.     

Reversible, metal-free hydrogen activation

Although reversible covalent activation of molecular hydrogen (H2) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C6H2Me3)2PH(C6F4)BH(C6F5)2 (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H2 at temperatures above 100 degrees C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C6H2Me3)2P(C6F4)B(C6F5)2 is stable and reacts with 1 atmosphere of H2 at 25 degrees C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism.     

Influence of carbonic anhydrase activity in terrestrial vegetation on the 18O content of atmospheric CO2

The oxygen-18 (18O) content of atmospheric carbon dioxide (CO2) is an important indicator of CO2 uptake on land. It has generally been assumed that during photosynthesis, oxygen in CO2 reaches isotopic equilibrium with oxygen in 18O-enriched water in leaves. We show, however, large differences in the activity of carbonic anhydrase (which catalyzes CO2 hydration and 18O exchange in leaves) among major plant groups that cause variations in the extent of 18O equilibrium (theta(eq)). A clear distinction in theta(eq) between C3 trees and shrubs, and C4 grasses makes atmospheric C18OO a potentially sensitive indicator to changes in C3 and C4 productivity. We estimate a global mean theta(eq) value of approximately 0.8, which reasonably reconciles inconsistencies between 18O budgets of atmospheric O2 (Dole effect) and CO2.     

Toward separation and purification of olefins using dithiolene complexes: an electrochemical approach

The complex Ni[S2C2(CF3)2]2 reacts with light olefins, including ethylene and propylene, selectively and reversibly. The reaction is not poisoned by hydrogen gas, carbon monoxide, acetylene, or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. The reversible reaction of olefins with Ni[S2C2(CN)2]2n (n = 0, -1, -2) can be controlled electrochemically, where the oxidation state-dependent binding and release of olefins are fast on the electrochemical time scale. The observed tolerance to poisons and controllable electrochemical reactivity present an alternative approach to the separation of olefins from complex streams.     

克拉玛依市10万亩减排林区固碳效益估算

[目的]量化克拉玛依市10万亩减排林区的固碳效益,为西北荒漠地区森林资源管理决策提供理论依据.[方法]调查克拉玛依市10万亩减排林区标准样地内树木的种类、株树、胸径、高度、盖度等,由此估算出该地区的固碳价值量及单位面积森林的固碳效益.[结果]克拉玛依市10万亩减排林区共有活立木蓄积量1.43×106m3,现存生物量2.21×106t,固定CO2实物量3.60× 106 t,折合纯C量9.81×105 t,固碳价值量2.15×108元,年均单位面积森林的固碳价值为32250元/ha.[结论]克拉玛依市10万亩减排林区森林生态系统在维持生物圈CO2和O2动态平衡、减缓温室效应等方面具有一定的积极作用.     

Cytidylic acid "a" trihydrate: structure and conformation

Cytidylic acid "a" (cytidine 2'-monophosphate) crystallizes in the triclinic space group P1 with two molecules of cytidine monophosphate (C(9)H(14)O(8)N(3)P) and six molecules of water in the unit cell. X-ray analysis of this crystal shows that in both molecules, the base is in the anti conformation, the ribose ring is C(2')-endo puckered, and the hydroxyl O(5') is gauche-gauche. The two molecules are linked by a short hydrogen bond through the phosphate oxygens.     

Global carbon sinks and their variability inferred from atmospheric O2 and delta13C

Recent time-series measurements of atmospheric O2 show that the land biosphere and world oceans annually sequestered 1.4 +/- 0.8 and 2.0 +/- 0.6 gigatons of carbon, respectively, between mid-1991 and mid-1997. The rapid storage of carbon by the land biosphere from 1991 to 1997 contrasts with the 1980s, when the land biosphere was approximately neutral. Comparison with measurements of delta13CO2 implies an isotopic flux of 89 +/- 21 gigatons of carbon per mil per year, in agreement with model- and inventory-based estimates of this flux. Both the delta13C and the O2 data show significant interannual variability in carbon storage over the period of record. The general agreement of the independent estimates from O2 and delta13C is a robust signal of variable carbon uptake by both the land biosphere and the oceans.     

HST and VLT investigations of the fragments of comet C/1999 S4 (LINEAR)

At least 16 fragments were detected in images of comet C/1999 S4 (LINEAR) taken on 5 August 2000 with the Hubble Space Telescope (HST) and on 6 August with the Very Large Telescope (VLT). Photometric analysis of the fragments indicates that the largest ones have effective spherical diameters of about 100 meters, which implies that the total mass in the observed fragments was about 2 x 10(9) kilograms. The comet's dust tail, which was the most prominent optical feature in August, was produced during a major fragmentation event, whose activity peaked on UT 22.8 +/- 0.2 July 2000. The mass of small particles (diameters less than about 230 micrometers) in the tail was about 4 x 10(8) kilograms, which is comparable to the mass contained in a large fragment and to the total mass lost from water sublimation after 21 July 2000 (about 3 x 10(8) kilograms). HST spectroscopic observations during 5 and 6 July 2000 demonstrate that the nucleus contained little carbon monoxide ice (ratio of carbon monoxide to water is less than or equal to 0.4%), which suggests that this volatile species did not play a role in the fragmentation of C/1999 S4 (LINEAR).