The Photochemistry of Diazomethane-Acetonitrile Mixtures. The Reaction of Methylene with Acetonitrile

The photochemistry of diazomethane-acetonitrile gaseous mixtures has been studied. Propionitrile was produced by the reaction of methylene radicals with acetonitrile. At lower pressures the product propionitrile decomposes and the measured decomposition rates are 1.14×10⁹ sec^?1 and 2.70×10⁸ sec^?1 at 3660 and 4358 Å, respectively.     

Density Functional Investigation of Methanethiol and Dimethyl Sulfide Adsorption on Zeolite

The density functional theory and cluster model methods have been employed to investigate the interactions between methanethiol, dimethyl sulfide and zeolites. The molecular complexes formed by adsorption of methanethiol or dimethyl sulfide on silanol H3SiOSi(OH)2OSiH3 with five coordination forms or four coordination forms, and complexes formed by interactions of Bronsted acid sites of bridging hydroxyl H3Si(OH)Al(OH)2OSiH3 with methanethiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carried out using the B3LYP hybrid method at 6-31 G (d,p) basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms between methanethiol and H3Si(OH)Al(OH)2OSiH3, dimethyl sulfide and H3Si(OH)Al(OH)2OSiH3, methanethiol and H3SiOSi(OH)2OSiH3, dimethyl sulfide and H3SiOSi(OH)2OSiH3 complexes have been comparatively studied. The calculated results showed the nature of interactions that led to the formation of all complexes was van der Waals force confirmed by an insignificant change of geometric structures and properties. The conclusions that methanethiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group were obtained on the basis of adsorption heat, the most stable adsorption models of a 6 ring structure for interaction between bridging hydroxyl and methanethiol, and a 7 ring structure for interaction between bridging hydroxyl and dimethyl sulfide.     

Effect of Water on Heterogeneous Catalytic Conversion of Dimethyl Sulfide into Methanethiol

In dry helium at 350°C and 0.1 MPa, dimethyl disulfide is catalytically converted to yield methanethiol and products of elimination such as ethylene and H₂S. Methanethiol decomposes into H₂S and dimethyl sulfide in the presence of acid catalysts, and water introduced into the system hinders this process and provides an increase in the catalyst stability.     

A Study of Chemically Activated Ethylmethylether

The decomposition rate of the chemically activated ethylmethylether produced from dimethyl ether-oxygen-diazomethane photolysis at 3660Å have been measured to be 2～5×10⁶ sec^?1. By comparing the pressure dependent variation of rate constants with the RRKM calculation results, the strong collision behavior of dimethylether and the gaussian energy distribution of singlet methylene are determined.     

Hydrogenolysis of Dimethyl Disulfide to Methanethiol in the Presence of Cobalt Sulfide Catalysts

The hydrogenolysis of dimethyl disulfide to methanethiol at T = 180–260°C and atmospheric pressure in the presence of supported cobalt sulfide catalysts has been studied. Cobalt sulfide on aluminum oxide exhibits a higher activity than that on a carbon support or silicon dioxide. The maximum reaction rate per gram of a catalyst is observed on an 8% Co/Al₂O₃ catalyst. At temperatures of up to 200°C and conversions up to 90%, methanethiol is formed with nearly 100% selectivity regardless of the cobalt content, whereas the selectivity for methanethiol under more severe conditions decreases because of its condensation to dimethyl sulfide.     

过渡金属改性的ZSM-5催化剂应用于甲硫醚转化制甲硫醇

负载过渡金属的ZSM-5 催化剂用于催化甲硫醚（DMS）转化成甲硫醇（MT）的反应. 实验结果表明,催化剂的甲硫醚转化率提高和甲硫醇选择性降低的趋势一样,都是以下顺序：Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. 表征结果表明,由于过渡金属阳离子（W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺）比Al³⁺活泼,而改性过程中W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺分别代替了部分Al³⁺,使得改性催化剂对DMS和MT的化学吸附作用更强. 过渡金属的引入使得ZSM-5总酸度增强,提高了C―S键的裂解能力,从而改进了催化转化DMS的能力. 研究结果发现,在转化DMS的过程中,金属活性位和酸性位之间通过强的协同效应起作用.     

The Photochemistry of Acetone: The Primary Decomposition of Acetone and Biacetyl Yields

In the photolysis of acetone at 265nm at 27°C the quantum yield of biacetyl has been determined to be 0.34 and the primary decomposition yield is evaluated to be about 0.68. The fraction of triplet acetone decomposed into methyl and acetyl radicals is estimated to be 0.14 at 313nm. The acetyl radicals undergo reaction to form biacetyl 50 times faster than decomposition to methyl radicals and carbon monoxide.     

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF2ClSH

Chemically activated CF₃SH, CFCl₂SH, and CF₂ClSH were formed through combination of SH and CF₃, CFCl₂, and CF₂Cl radicals, respectively. The SH radical was prepared by abstraction of an H‐atom from H₂S by the halocarbon radical produced during photolysis of (CF₃)₂C=O, (CFCl₂)₂C=O, or (CF₂Cl)₂C=O. 1,2‐HX (X = F, Cl) elimination reactions were observed from CF₃SH, CFCl₂SH, and CF₂ClSH with products detected by GC‐MS. The combination reaction of CF₂Cl radicals with SH radicals prepared CF₂ClSH molecules with approximately 318 kJ/mol of internal energy. The experimental rate constants for elimination of HCl and HF from CF₂ClSH were 3 ± 3 × 10¹⁰ and 2 ± 1 × 10⁹ s^?1, respectively. Comparison to Rice–Ramsperger–Kassel–Marcus (RRKM) calculated rate constants assigned the threshold energies as 171 ± 12 and 205 ± 12 kJ/mol for the unimolecular elimination of HCl and HF, respectively. Theoretical calculations using the B3PW91, MP2, and M062X methods with the 6311+G(2d,p) and 6‐31G(d',p') basis sets established that for a specific method the threshold energies differ by only 4 kJ/mol between the two different basis sets. There was wide variation among the three methods, but the M062X approach appeared to give threshold energies closest to the experimental values. Chemically activated CF₃SH and CFCl₂SH were also prepared with about 318 kcal mol^?1 of internal energy, and the HX (X = F, Cl) elimination reactions were observed. Only HCl loss was detected from CFCl₂SH, but the rate was too fast to measure with our kinetic method; however, based on our detection limit the HF elimination channel is at least 50 times slower.     

The Characteristics of Mechanically Activated Mixtures of Copper Hydroxocarbonate With Aluminium

The chemical and physical processes occurring during grinding of copper hydroxocarbonates mixtures with aluminium were studied. A planetary ball mill was used. A thermogravimetry and X-ray powder diffraction method allowed to determine the composition of solid products after mechanical activation. The amount of the Cu₂(OH)₂CO₃ undecomposed andAl₂O₃⋅3H₂O, CuO, Al₂O₃, Cu⁰, Cu_xAl_y alloys and remained Al0 in the systems is strongly dependent on the duration of grinding and on the proportion of components. The comparative results are presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Photochemistry of Aliphatic Nitroxide Radicals Grafted onto Activated Aerosil Surface

The mechanism of photoinduced transformations of nitroxide radicals SiON(O^·)CH₃ (I) and SiOCH₂N(O^·)CH₃ (II) obtained on the activated aerosil surface was studied. The nitroxides were photolyzed with 436-nm light at 77 K. It was shown that the action of light in the long-wavelength absorption band corresponding to the n–* transition resulted in the dissociation of the O–N or C–N bond in radicals I or II, respectively. The quantum yields of these reactions were found to be 0.6 and 0.002, respectively.     

On the Separation of Timescales in Chemically Activated Reactions

Chemically activated reactions are important in describing the composition of reactive gases including flames, planetary atmospheres, and the interstellar medium (ISM). In a chemically activated reaction, two reactants combine to populate a vibrationally excited well that can undergo unimolecular transformations (isomerization, dissociation) or be thermalized through collisions with the bath gas. Once a well has been thermalized, it may still have sufficient energy to undergo further unimolecular reaction, in a purely thermal process. If the timescale for the thermally activated process is sufficiently short, such that it approaches that of the chemically activated reaction, the two concurrent processes become inseparable and the value of the phenomenological rate coefficient is no longer obvious. Here, we introduce the thermal decay (TD) procedure to determine phenomenological rate coefficients for chemically activated reactions proceeding on timescales approaching those of thermal reaction, principally for use in stochastic master equation simulations of multiple‐well multiple‐channel unimolecular reaction processes. By fitting the thermal decay of the initially activated well to a first‐order kinetic model, the would‐be thermal yield can be eliminated so as to arrive at the chemically activated component in a reliable and objective fashion. This technique is demonstrated here for the reaction of 1,3,6‐heptatriyne with H using the MultiWell code and a 16‐well 33‐channel C₇H₅ reaction model. A computer program implementing the TD method and for postprocessing of MultiWell output data, PPM, is provided.     

脱硫化氢活性炭的再生方法研究

采用了溶剂再生法和气体再生法对脱硫化氢失活后的活性炭进行再生,溶剂再生时所用的溶剂为H2O2溶液、HNO3溶液以及NaOH溶液。结果表明,NaOH溶液不能使活性炭得到再生,而H2O2溶液、HNO3溶液能够通过氧化的方法使活性炭得到再生。气体再生时所用的气体分别为高纯N2,含20%O2的N2,H2,它们再生的原理分别是热再生,通过氧化单质硫再生和通过还原单质硫再生。再生效果最好的是30%的HNO3溶液和H2,它们能将活性炭孔道内的单质硫分别脱出69.8%和81.2%,再生后的活性炭中硫容量能达到原来的70%以上。再生后活性炭的比表面积和pH值是再生性能的两个重要指标。     

荧光素酶法测定活性污泥中的ATP

选择了４种不同的提取剂，对曝气池活性污泥的腺苷三磷酸进行提取，并用荧光素酶法进行了测定。结果表明，不同提取剂所提取的ＡＴＰ量有很大不同；同一提取剂对不同水样ＡＴＰ的提取效果也不同。     

Graphene Oxide Modified Chemically Activated Graphite Electrodes for Detection of microRNA

In our study, graphene oxide (GO) modified graphite electrodes were used for sensitive and selective impedimetric detection of miRNA. After chemical activation of pencil graphite electrode (PGE) surface using covalent agents (CA), GO modification was performed at the surface of chemically activated PGE. Then, CA‐GO‐PGEs were applied for impedimetric miRNA detection. The microscopic and electrochemical characterization of CA‐GO‐PGEs was performed by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The optimization of experimental conditions; such as GO concentration, DNA probe concentration and miRNA target concentration was performed by using EIS technique. After the hybridization occurred between miRNA‐34a RNA target and its complementary DNA probe, the hybrid was immobilized onto the surface of CA‐GO‐PGEs. Then, the impedimetric detection of miRNA‐DNA hybridization was performed by EIS. The selectivity of our assay was also tested under the optimum experimental conditions.     

紫外光分解硫化氢制氢的研究

以10W低压汞灯(特征谱线波长,λ=253.7nm,简称UVC)作为光源,硫化钠的水溶液作为反应介质,进行了UVC直接分解硫化氢制氢反应(简称UVC-H₂S-H₂)的研究.考察了反应介质中硫的存在形式、硫化钠的浓度、反应介质pH值以及连续通入硫化氢的流量等反应条件对UVC-H₂S-H₂的影响.实验结果表明,UVC可以在无催化剂条件下直接分解硫化氢制氢.当以0.6mol/L硫化钠水溶液为反应介质,以25mL/h流量连续向反应介质中通入硫化氢时,UVC-H₂S-H₂产氢速率可达3.0mL/W·h.     

Decomposition of Gaseous Sulfide Compounds in Air by Pulsed Corona Discharge

The effectiveness of applying a pulsed corona discharge to the destruction of olfactory pollution in air was investigated. This paper presents a comparative study of the decomposition of three representative sulfide compounds in diluted concentrations: hydrogen sulfide (H₂S), dimethyl sulfide (DMS), and ethanethiol (C₂H₅SH), which could be completely removed when a sufficient but reasonable energy density was deposited in the gas. DMS showed the lowest energy cost (around 30 eV/molecules); C₂H₅SH and H₂S had an EC of respectively 45 eV and 115 eV. The efficiency of the non-thermal plasma process increased with decreasing the initial concentration of sulfide compounds, while the energy yield remained almost unchanged. SO₂ was the only identified byproduct of H₂S decomposition, but the sulfur balance suggests the formation of undetected SO₃. The byproducts analyzed during the degradation of DMS and C₂H₅SH enabled to propose a reaction mechanism, starting with radical attack and breaking of C–S bonds.     

Adsorption Behaviors of CO2 and NH3 on Chemically Surface-Treated Activated Carbons

The adsorption characteristics of activated carbon treated with 30 wt% HCl and 30 wt% NaOH were investigated. The acid and base values were determined by Boehm's method and the surface structures were studied by the BET method with N2 adsorption and iodine adsorption capacity. Also the adsorption properties of the activated carbons treated with acid and base chemical solutions were investigated with CO2 and NH3 adsorptions. Different adsorption behaviors of CO2 and NH3 on the modified activated carbons were observed, even though the physical surfaces of the activated carbons (i.e., specific surface area, pore size, and pore volume) were not significantly changed. Copyright 1999 Academic Press.