On the reactivity of metal and organometallic halides toward R3Sn?O?SnR3 systems

Interaction of metallic salts (M = Hg, Sb, and Te) with bis(triorganotin)oxide, (R₃Sn)₂O, where (R = C₆H₅, p‐CH₃C₆H₄, and cyclo‐C₆H₁₁) at room temperature proceeded with the simultaneous cleavage of the Sn C and Sn O bonds, invariably yielding R₂SnO along with other products. Thus the treatment of HgX₂ (X = Cl, CN, SCN) with (R₃Sn)₂O resulted in the formation of polymeric diorganotin oxide R₂SnO along with R₃SnX and RHgX derivatives. The reaction of SbCl₃ with (R₃Sn)₂O was found to give R₂SnO, R₃SnCl, and RSbCl₂, whereas interaction with SbCl₅ provided R₂SnO, R₂SnCl₂, and R₂SbCl₃. Treatment of TeCl₄ with (R₃Sn)₂O provided R₂SnO, R₃SnCl, and RTeCl₃ at room temperature. At reflux temperature, reaction of PhTeCl₃ with (R₃Sn)₂O yielded R₂SnO, R₃SnCl, and mixed diorganotellurium dichloride, RPhTeCl₂. The course of reaction indicated the instability of Sn O Sn system proceeding via a four‐centered mechanism, providing organometallic compounds in profitable yield. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:278–283, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20547     

用T-jump/FTIR研究MnCP、NiCP和PbCP的快速热分解(英)

0IntroductionCarbohydrazideisahydrazinederivativewithwhitecrystalofstrongreducingbehaviors.Becauseithasmanycoordinationatoms(fournitrogenatomsandoneoxygenatom),carbohydrazidecan,therefore,beusedasmultidentateligand.Itscoordinationcom鄄poundiswidelyusedint…     

Synthesis and Structure of Cyclic Selenium Oxide SeVISe2IVO7

Nitromethane is the only presently known organic solvent for highly reactive selenium trioxide (SeO₃)₄. The stability of the solutions is limited and the beginning of the reaction between both components depends significantly on concentration and temperature. The nitromethane solvate of cyclic triselenium heptoxide Se₃O₇ · CH₃NO₂ is the major solid product at the temperature 20–30°C and concentration range 3–20% SeO₃. Crystal and molecular structure of this compound was determined by X-ray structure analysis and vibrational spectroscopy. The solvating molecule CH₃NO₂ is removable from Se₃O₇ · CH₃NO₂ in vacuo. If reaction temperature does not exceed 10°C, selenium pentoxide (Se₂O₅)_n is formed instead of Se₃O₇ · CH₃NO₂. Dinitrosyl triselenate (NO)₂Se₃O₁₀, nitrosyl hydrogendiselenate NOHSe₂O₇, nitrosyl hydrogenselenate NOHSeO₄, nitrosyl hydrogenselenatoselenite NOHSe₂O₆ and selenium dioxide (SeO₂)_n were further identified in the solid reaction products. The selenic and/or oligoselenic acids remains in the nitromethane solution. CO₂ and N₂O₃ were found as gaseous products.     

The Direct Partial Oxidation of Methane to Dimethyl Ether over Pt/Y2O3 Catalysts Using an NO/O2 Shuttle

Using a mixture of NO + O₂ as the oxidant enabled the direct selective oxidation of methane to dimethyl ether (DME) over Pt/Y₂O₃. The reaction was carried out in a fixed bed reactor at 0.1 MPa over a temperature range of 275–375 °C. During the activity tests, the only carbon‐containing products were DME and CO₂. The DME productivity (μmol g_cat^?1 h^?1) was comparable to oxygenate productivities reported in the literature for strong oxidants (N₂O, H₂O₂, O₃). The NO + O₂ mixture formed NO₂, which acted as the oxygen atom carrier for the ultimate oxidant O₂. During the methane partial oxidation reaction, NO and NO₂ were not reduced to N₂. In situ FTIR showed the formation of surface nitrate species, which are considered to be key intermediate species for the selective oxidation.     

Studies of the Reaction Behavior of Nitryl Compounds Towards Azides: Evidence for Tetranitrogen Dioxide,N4O2

The reaction behavior of NaN₃, AgN₃, and Me₃SiN₃ towards FNO₂, CINO₂, NO₂SbF₆, and NO₂BF₄ was investigated. At -30°C or below in a solvent-free system sodium azide did not react with CINO₂, NO₂BF₄, or NO₂SbF₆. Below -30°C silver azide did not react either with neat C1NO₂. Treatment of Me₃SiN₃ with pure C1NO₂ led to the formation of C1N₃, N₂O, and Me₃SiOSiMe₃. A mechanism for this reaction has been proposed. Pure chlorine azide was isolated by fractional condensation and identified by its low-temperature Raman spectrum (liquid state). The reaction of Cp₂Ti(N₃)₂ with C1NO₂ also yielded C1N₃ as the only azide-containing reaction product. Treatment of FNO₂ with NaN₃ at temperatures as low as -78°C always ended in an explosion which was probably due to the formation of FN₃ as one of the reaction products. The reaction of NO₂SbF₆ with NaN₃ in liquid CO₂ (-55°C· T· -35°C) as the solvent afforded a new azide species which was stable at low temperature in solution only and was investigated by means of low-temperature Raman spectroscopy. The obtained vibrational data give strong evidence for the presence of tetranitrogen dioxide, N₄O₂, which can be regarded as nitryl azide (NO₂N₃). The structure and vibrational frequencies of N₄O₂ were computed ab initio at correlated level (MP2/6-31 + G^*). In liquid xenon (-100°C· T· -60°C) NaN₃ did not react with NO₂SbF₆. A previous literature report on the preparation of N₄O₂ could not be established.     

Effect of conversion of NO2 into no on the catalytic reduction of NO2 with C3H6 in excess O2

During the reduction of NO₂ by C₃H₆ in O₂ over alumina-supported Au, Rh and Pt it was found that three parallel reactions take place,i.e., reduction of NO₂ to N₂ and N₂O, partial decomposition of NO₂ to NO and oxidation of C₃H₆ to CO and CO₂. In the absence of C₃H₆, the NO₂→NO+O₂ reaction reaches a fast equilibrium on Rh and Pt but not on Au and γ-Al₂O₃. Addition of C₃H₆ to the NO₂+O₂ mixture leads to the formation of NO above equilibrium conversion levels.     

The cooperative effect of Zn on Co/HZSM-5 catalyst for NO reduction with methane

The cooperation of Zn and Co in the Zn-Co/HZSM-5 catalyst was investigated. NO was selectively reduced by CH4 to N₂ in the presence of excess O₂, and the catalytic activity depended on both the activation of CH4 and the adsorption properties of NO_x. It was found that the addition of Zn could effectually heighten the selectivity of methane to NO_x. The results of H₂-TPR, NH₃-TPD and XPS proved that addition of Zn into Co/HZSM-5 could inhibit the formation of bulk Co₃O₄ on the outer surface of the catalyst. Reducing the bulk Co₃O₄ would restrain the combustion of methane and improve the selectivity of methane to NO_x, which was very consistent with the experimental results. MS-TPD results showed that Zn contributed the form of NO₂ and strengthened its adsorption on the Co/HZSM-5 catalyst. So the reaction mechanism is proposed to occur via two successive elementary steps. First NO is oxidized to NO₂ on the dispersed CoOx sites or Co²⁺ active sites; then NO₂ is adsorbed on Zn²⁺ sites, and further reacts with methane on proton acid sites. The key step is the adsorption of NO₂. Zn directly participates in the reaction by adsorption of NO₂.     

Stratospheric chemical ionization mass spectrometry: nitric acid detection by different ion molecule reaction schemes

Detailed height profiles of stratospheric nitric acid mixing ratios have been derived with a baloon borne chemical ionization mass spectrometer by applying several ion molecule reaction schemes, each associated to a specific and selective ion source. These ions (CO₃⁻, Cl_n⁻, CF₃O⁻, and CF₃O⁻H₂O) give rise to specific product ions (mainly CO₃⁻HNO₃, NO₃⁻HCl, NO₃⁻HF, and CF₃O⁻HNO₃) upon reaction with ambient nitric acid molecules. This paper reports on the instrumental details as well as on the results obtained during two balloon flights with the instrument. Within the accuracy of the measurements, the nitric acid height profiles obtained with the three different ion sources are in good agreement with one another as well as with literature data.     

TEA CO2 laser-induced reaction of CH3NO2 with CF2HCl: A mechanistic study

Dissociation of nitromethane has been observed when a mixture of CF₂HCl and CH₃NO₂ is irradiated using pulsed TEA CO₂ laser at 9R (24) line (1081 cm^-1), which is strongly absorbed by CF₂HCl but not by CH₃NO₂. Under low laser fluence conditions, only nitromethane dissociates, whereas at high fluence CF₂HCl also undergoes dissociation, showing that dissociation occurs via the vibrational energy transfer processes from the TEA CO₂ laser-excited CF₂HCl to CH₃NO₂. Time-resolved infrared fluorescence from vibrationally excited CF₂HCl and CH₃NO₂ molecules as well as UV absorption of CF₂ radicals are carried out to elucidate the dynamics of excitation/dissociation and the chemical reactions of the dissociation products.     

CH3O与ClO双自由基反应机理的量子化学研究

在QCISD(T)/6-311＋G(d,p)//B3LYP/6-311＋G(3df,3pd)水平上, 对CH₃O与ClO双自由基反应进行了理论研究. 结果表明, 该反应共有三个反应通道, 产物分别为HOCl＋CH₂O, CH₂O₂＋HCl和CH₃Cl＋O₂(¹Δ). 不论从动力学角度, 还是从热力学角度看, 形成产物HOCl＋CH₂O的通道均是最有利的, 因此为主要反应通道, 这与实验观察到的结果是一致的.     

Product Determination of Gaseous Radical Reactions Using Matrix Isolation-Ftir Detection

The matrix isolation technique with Fourier transform infrared detection has been applied to determine the products of gaseous radical reactions. The gas phase reactions were carried out in a discharge flow system and about 1% of the gas mixture was deposited onto a low temperature target through a pinhole. A differential pumping scheme was employed to maintain the pressure of the cryosystem below 10^?5 torr while that of the flow system was kept at about 2 torr. Species including HO₂ (from the H+O₂ reaction), ClO₂ (from the Cl+O₂ reaction) and ClO (from the Cl+O₃ reaction) have been produced in the gas phase and were successfully trapped in matrices and detected with an FTIR spectrometer. In addition, both HCl and HOCl have been detected as the reaction products from the gaseous ClO+HO₃ reaction. The production of HCl from the ClO+HO₂ reaction may have a significant impact on catalytic ozone destruction in the atmosphere.     

Ni基催化剂催化燃油重整耦合选择性催化还原NOx反应

分别以La₂O₂CO₃, CeO₂, ZrO₂和Al₂O₃为载体, 采用浸渍法制备了Ni基重整催化剂, 并以正十二烷模拟车载燃油进行催化重整反应以同时制备小分子碳氢化合物(HCs)和H₂, 考察了其在4wt%Ag/Al₂O₃上选择性催化还原(HC-SCR)氮氧化物(NO_x)的性能. 采用N₂吸附-脱附、X射线粉末衍射、H₂程序升温还原和热重等手段对Ni基催化剂进行了表征. 结果表明, 随着重整催化剂氧化还原性能增强, 产物中H₂浓度增加, 可参与SCR反应的HCs含量减少, 从而导致重整-SCR耦合体系上NO_x净化活性温度窗口向低温移动, NO_x最高转化率降低. Ni/ZrO₂+Ag/Al₂O₃耦合体系中H₂/HCs符合SCR反应所需的最优比例, 在柴油车典型排气温度范围内表现出良好的NO_x净化能力. 同时, 在Ni/ZrO₂+Ag/Al₂O₃耦合体系上考察了其燃油重整-SCR的活性稳定性. 结果显示, 重整催化剂的耐久性有待进一步提高.     

Diesel soot oxidation by nitrogen dioxide,oxygen and water under engine exhaust conditions: Kinetics data related to the reaction mechanism

Experimental studies on diesel soot oxidation under a wide range of conditions relevant for modern diesel engine exhaust and continuously regenerating particle trap were performed. Hence, reactivity tests were carried out in a fixed bed reactor for various temperatures and different concentrations of oxygen, NO₂ and water (300–600 °C, 0–10% O₂, 0–600 ppm NO₂, 0–10% H₂O). The soot oxidation rate was determined by measuring the concentration of CO and CO₂ product gases. The parametric study shows that the overall oxidation process can be described by three parallel reactions: a direct C–NO₂ reaction, a direct C–O₂ reaction and a cooperative C–NO₂–O₂ reaction. C–NO₂ and C–NO₂–O₂ are the main reactions for soot oxidation between 300 and 450 °C. Water vapour acts as a catalyst on the direct C–NO₂ reaction. This catalytic effect decreases with the increase of temperature until 450 °C. Above 450 °C, the direct C–O₂ reaction contributes to the global soot oxidation rate. Water vapour has also a catalytic effect on the direct C–O₂ reaction between 450 °C and 600 °C. Above 600 °C, the direct C–O₂ reaction is the only main reaction for soot oxidation. Taking into account the established reaction mechanism, a one-dimensional model of soot oxidation was proposed. The roles of NO₂, O₂ and H₂O were considered and the kinetic constants were obtained. The suggested kinetic model may be useful for simulating the behaviour of a diesel particulate filter system during the regeneration process.     

Methane Reforming with Carbon Dioxide on the Co/α-Al2O3 Catalyst: The Formation, State, and Transformations of Surface Carbon

The interactions of oxidized and reduced Co/-Al₂O₃ (4 wt % CoO) with H₂, CH₄, CO₂, and O₂ and their mixtures are studied in flow and pulse regimes using a setup involving a DSC-111 differential scanning calorimeter and a system for chromatographic analyses. It is shown that treatment with hydrogen at 700°C results in the partial reduction of cobalt oxide to Co. Methane poorly reacts with the oxidized catalyst but readily reacts with the reduced catalyst to form H₂ and surface carbon. The initial surface carbon transforms into other forms, which block the cobalt surface to different extents and differ in the heats of reaction with CO₂. Carbon dioxide may react with the surface carbon to form CO (rapidly) and with metallic Co to form CO and CoO (slowly). Thus, the main route of methane reforming with carbon dioxide on Co/-Al₂O₃ is the dissociative adsorption of CH₄ to form surface carbon and H₂ and the reaction of surface carbon with CO₂ to form CO via the reverse Boudouard reaction.     

Linear-Reactor-IR.-Matrix and Microwave Spectroscopy of the System O3/NO2/(Z)-2-Butene

Investigation of the formation of complex reaction products in the gas-phase system O₃/NO₂/(Z)-2-butene by combination of linear reactors with IR. matrix and microwave Stark Spectroscopy is reported. Besides the polyatomic products observed earlier in the gas-phase ozonolysis of (Z)-2-butene, the following products were identified; N₂O₅, HNO₃, HNO₄, CH₃NO₂, CH₃ONO, CH₃COONO₂ and CH₃COO₂NO₂ (peroxyacetyl nitrate, PAN). Matrix IR. spectra of N₂O₅, HNO₃. CH₃COONO, CH₃COONO₂ required for reference purposes are presented. It is shown that PAN-formation occurs already in the absence of light. A reaction scheme is proposed for explanation of the observed complex NO_x-containing products, which assumes methyldioxirane as a central intermediate. Particular reaction steps of the scheme will be discussed, including thermochemical estimates of reaction enthalpies.     

Influence of weakly bound adduct ions on breath trace gas analysis by selected ion flow tube mass spectrometry (SIFT-MS)

This paper describes how weakly bound adduct ions form when the precursor ions used in selected ion flow mass spectrometry, SIFT-MS, analyses, viz. H₃O⁺, NO⁺ and O₂⁺, associate with the major components of air and exhaled breath, N₂, O₂ and CO₂. These adduct ions, which include H₃O⁺N₂, H₃O⁺CO₂, NO⁺CO₂, O₂⁺O₂ and O₂⁺CO₂, are clearly seen when dry air containing 5% CO₂ (typical of that in exhaled breath) is analysed using SIFT-MS. These adduct ions must not be misinterpreted as characteristic product ions of trace gases; if so, serious analytical errors can result. However, when exhaled breath is analysed these adduct ions are partly removed by ligand switching reactions with the abundant water molecules and the problems they represent are alleviated. But the small fractions of the adduct ions that remain in the SIFT-MS spectra, and especially when they are isobaric with genuine characteristic product ion of breath trace gases, can result in erroneous quantifications; such is the case for H₃O⁺N₂ interfering with breath ethanol analysis and H₃O⁺CO₂ with breath acetaldehyde analysis. However, these difficulties can be overcome when the isobaric adduct ions are properly recognised and excluded from the analyses; then these two important compounds can be properly quantified in breath. The presence of O₂⁺CO₂ in the product ion spectra interferes with the analysis of CS₂ present at low levels in exhaled breath. It is likely that similar problems will occur as other trace compounds are detected in exhaled breath when consideration will have to be given to the possibility of overlapping between their characteristic product ions and ions produced by hitherto unknown reactions. Similar problems are evident in other systems; for example, H₃O⁺CH₄ adduct ions are observed in both SIFT-MS analyses of methane rich mixtures like biologically generated waste gases and in model planetary atmospheres.     

The removal of styrene using a dielectric barrier discharge (DBD) reactor and the analysis of the by-products and intermediates

As a kind of volatile organic compound, styrene is a typical industrial pollutant with high toxicity and odorous smell. In this study, the removal of malodorous styrene simulation waste gas was carried out in a self-made wire-tube dielectric barrier discharge reactor. The decomposition efficiency of the reaction was investigated under different applied voltages and flow rates. The results showed that nearly 99.6 % of styrene could be removed with a concentration of 3,600 mg/m³ and the applied voltage of 10.8 kV. However, the selectivity of CO₂ and CO showed that the mineralization efficiency of styrene was less than 25 %. The by-products of the reaction, including O₃, NO _x and other intermediates, were also detected and analyzed under different applied voltages. The relationships between the applied voltage and the quantity of final product (CO₂) and by-products (intermediate organics, NO _x , O₃) were investigated. The reaction mechanism was also described according to the bond energy and the intermediates that formed.     

Metal oxide semiconductor sensors for determination of reactive gas impurities in air

Characteristics of metal oxide semiconductor sensors intended for measuring O₃, NO _x , Cl₂, C1O₂, and HCl microconcentrations were discussed. Specific features of detection of these microimpurities with semiconductor sensors were determined. The size of signal generated by sensors with WO₃-, ZnO-, and In₂O₃-based sensing layers was examined in relation to the O₃, NO _x , Cl₂, C1O₂, and HCl concentration. The sensitivities exhibited by the semiconductor sensors with respect to target impurities make them suitable for measuring their maximum permissible concentrations in sanitary zones and for monitoring background ozone level in atmosphere. Examples of application of gas analyzers based on semiconductor sensors in determination of gas impurities in the open atmosphere were given.     

Laboratory investigations of negative ion molecule reactions of propionic,butyric, glyoxylic,pyruvic, and pinonic acids

We have carried out laboratory measurements of gas-phase ion-molecule-reactions of several negative ion species with propionic, butyric, glyoxylic, pyruvic, and pinonic acids. A flow reactor operating at a temperature of 293 ± 3 K and total gas pressures of 1.5 hPa, 9 hPa, or 40 hPa were used. The negative reagent ion species investigated included CO₃⁻, CO₃⁻H₂O, NO₃⁻, NO₃⁻H₂O, NO₂⁻, NO₂⁻H₂O, and O₃⁻. The reactions were found to proceed either via proton transfer, switching, or clustering. A new proton transfer channel leading to alkylperoxy carboxylate radicals (R_−H(OO·)COO⁻) was observed for propionic, butyric, and pinonic acids.     

Determination of oxygen in oxides by carrier gas hot extraction analysis with simultaneous COx detection

The determination of oxygen by carrier gas hot extraction is the most popular method for oxygen analysis, but its application to high oxygen contents in oxides requires a critical look at the basic assumptions of the method. The process was studied for various oxides (Al₂O₃, Bi₂O₃, Cr₂O₃, Fe₂O₃, MoO₃, NiO, TiO₂, WO₃, Y₂O₃, and ZrO₂) using a modern analyser with IR-detectors for CO₂ and CO. There was a difference specific to oxides that must be known to get the required analytical results with high precision and accuracy. High amounts of CO₂ were formed particularly from Bi₂O₃, Fe₂O₃, MoO₃, NiO, and WO₃. The reaction rate can be controlled with delayed heating of the furnace, so that an oxide sample weight of up to 100 mg can be used. Received: 13 April 1999 / Revised: 24 June 1999 / Accepted: 28 June 1999