不良溶剂对甲基丙烯酸丁酯ATRP反应的影响     

刘燕孟庆民  许风玲王志 张以群 《华东地质学院学报》2005,28(3):252-254

以2-溴代异丁酸乙酯[2-（EiB）-Br]为引发剂,CuBr/2,2^1-bpy为催化体系,进行了甲基丙烯酸丁酯（BMA）在丙酮、丙酮/甲醇、丙酮/水中的原子转移自由基聚合,研究了溶剂、温度对聚合反应活性特征的影响.结果表明,水或甲醇的加入,使反应速率有所增加,水的影响最大;在其它反应条件相同时,水或甲醇对反应的影响在低温时更为明显.  相似文献   

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH     

S. Sørensen  H. Falbe-Hansen  M. Mangoni  J. Hjorth  N. R. Jensen 《Journal of Atmospheric Chemistry》1996,24(3):299-315

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.  相似文献   

Changing trends in tropospheric methane and carbon monoxide: A sensitivity analysis of the OH-radical     

Han Van Dop  Maarten Krol 《Journal of Atmospheric Chemistry》1996,25(3):271-288

A sensitivity analysis is performed in order to study recently observed changes in atmospheric methane and carbon monoxide trends. For the analysis we have adapted a one-dimensional transport/chemistry model in order to comply with changes in vertical transport, stratosphere-troposphere flux of ozone, the water vapour cycle and the short-wave radiative transfer. In addition we have formulated an improved relationship which expresses the steady state OH concentration in terms of longer lived compounds which has a fair agreement with the one-dimensional model results. An analysis of the observed changes and trends in methane and carbon monoxide shows that both emissions and changes in global OH concentrations can be main causes for the observed changes. Average methane emissions have slowed down, particularly in the NH, in the last five years, though perhaps not very significantly. Carbon monoxide emissions are decreasing faster in the last couple of years than in the period 1983–1990. The study suggests that climate fluctuations (tropospheric water vapour, temperature and convective activity) and the stratospheric ozone depletion (tropospheric UV radiation) have a significant influence on tropospheric composition and thus on trends in methane and carbon monoxide concentrations.The IMAU is partner in the Netherlands Centre for Climate Research (CCR).  相似文献   

萤石颜色与自由基关系的电子自族共振（ESR）研究   总被引：1，自引：0，他引：1  

唐荣炳  温桂兰 《矿物岩石地球化学通报》1996,(4)

萤石颜色与自由基关系的电子自族共振（ＥＳＲ）研究唐荣炳，温桂兰（中国科学院地球化学研究所，贵阳５５０００２）（中国科学院广州地球化学研究所，广州５１０６４０）关键词萤石，顺磁离子，自由基长期以来，对矿物颜色的研究，先是定性观察和分类，再是应用光的吸收...  相似文献   

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH     

F. Nolting  W. Behnke  C. Zetzsch 《Journal of Atmospheric Chemistry》1988,6(1-2):47-59

The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO _x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10^–12 cm³ s^–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10^–17 cm³ s^–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.  相似文献   

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions   总被引：1，自引：0，他引：1  

J. Alistair Kerr  David W. Stocker 《Journal of Atmospheric Chemistry》1986,4(2):253-262

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.  相似文献   

Methane,carbon monoxide and methylchloroform in the southern hemisphere   总被引：1，自引：0，他引：1  

P. J. Fraser  P. Hyson  R. A. Rasmussen  A. J. Crawford  M. A. K. Khalil 《Journal of Atmospheric Chemistry》1986,4(1):3-42

New observational data on CH₄, CO and CH₃CCl₃ in the southern hemisphere are reported. The data are analysed for long term trends and seasonal cycles. CH₃CCl₃ data are used to scale the OH fields incorporated in a two dimensional model, which in turn, is used to constrain the magnitude of a global CH₄ source function. The possible causes of observed seasonality of CH₃CCl₃, CH₄ and CO are identified, and several other aspects of observed CH₄ variability are discussed.Possible future research directions are also given.  相似文献   

The NO2-O3 system at sub-ppm concentrations: Influence of temperature and relative humidity     

P. W. C. Verhees  E. H. Adema 《Journal of Atmospheric Chemistry》1985,2(4):387-403

The stoichiometry and kinetics of the reaction of NO₂ with O₃ at sub-ppm concentration level have been investigated as a function of temperature and relative humidity. The experiments were performed in a continuous flow reactor using chemiluminescent and wet chemical methods of analysis.The rate constant found can be described by the Arrhenius expression: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiaaik% dacaGGUaGaaGyoaiaaiEdacqGHXcqScaaIWaGaaiOlaiaaigdacaaI% 0aGaaiykaiabgEna0kaaigdacaaIWaWaaWbaaSqabeaacqGHsislca% aIXaGaaG4maaaakiaabwgacaqG4bGaaeiCaiaacIcadaWcgaqaaiaa% cIcacqGHsislcaaIYaGaaGOnaiaaikdacaaIWaGaeyySaeRaaGyoai% aaicdacaGGPaaabaGaamivaiaacMcacaqGGaGaae4yaiaab2gadaah% aaWcbeqaaiaabodaaaGccaqGGaWaaSGbaeaacaqGTbGaae4BaiaabY% gacaqGLbGaae4yaiaabwhacaqGSbGaaeyzamaaCaaaleqabaGaaeyl% aiaabgdaaaaakeaacaqGZbWaaWbaaSqabeaacaqGTaGaaeymaaaaaa% aaaaaa!62A3!\[(2.97 \pm 0.14) \times 10^{ - 13} {\text{exp}}({{( - 2620 \pm 90)} \mathord{\left/ {\vphantom {{( - 2620 \pm 90)} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}} \right. \kern-\nulldelimiterspace} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}\] and are independent of the relative humidity. As commonly encountered in previous studies a lower-than-two reaction stoichiometry is observed.Heterogeneous reactions occurring at the reactor wall seem to be essential in the reaction mechanism. The NO₃ wall conversion to NO₂ and the N₂O₅ wall scavenging in the presence of H₂O are suggested to account for the observed stoichiometric factors.  相似文献   

Electron paramagnetic resonance characteristics of the humic acids from a podzol     

M.V. Cheshire  B.A. Goodman  D.B. McPhail  G.P. Sparling 《Organic Geochemistry》1985,8(6):427-440

A study has been made of solid and solution electron paramagnetic resonance (EPR) spectra of humic acids from different horizons in a podzolic soil. Hyperfine splitting was observed in the solution spectra of humic acids from all horizons and depended on the strength of alkali and the period of dissolution. The upper organic horizons L, F and O₁ contained humic acids with some spectral characteristics in common with lignin. Humic acid from the lower horizons showed different spectra. At least 5 different radical signals were present.  相似文献   

Effect of pH on photo-oxidation of dissolved organic carbon by hydroxyl radicals in a coloured, softwater stream   总被引：3，自引：1，他引：2  

Lewis A. Molot  Jeff J. Hudson  Peter J. Dillon  Sean A. Miller 《Aquatic Sciences - Research Across Boundaries》2005,67(2):189-195

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