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1.
The rate constants k1 for the reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm3 reaction chamber with either CHF2Cl or CH2FCF3 as a reference compound. OH radicals were produced by UV photolysis of an O3–H2O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k1 (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10?15 cm3 molecule?1 s?1 (FP‐LIF method) and (1.72 ± 0.07) × 10?15 cm3 molecule?1 s?1 (LP‐LIF method), whereas the K1 (298 K) values determined by the relative method were (1.87 ± 0.11) × 10?15 cm3 molecule?1 s?1 (CHF2Cl reference) and (2.12 ± 0.11) × 10?15 cm3 molecule?1 s?1 (CH2FCF3 reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K1 = (4.71 ± 0.94) × 10?13 exp[?(1630 ± 80)/T] cm3 molecule?1 s?1. Using kinetic data for the reaction of tropospheric CH3CCl3 with OH radicals [k1 (272 K) = 6.0 × 10?15 cm3 molecule?1 s?1, tropospheric lifetime of CH3CCl3 = 6.0 years], we estimated the tropospheric lifetime of CF3CF2CF2CF2CF2CHF2 through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004  相似文献   
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Application of stir bar sorptive extraction for wine analysis   总被引:4,自引:0,他引:4  
Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used.  相似文献   
4.
High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first example of an exo-selective cycloaddition. [reaction: see text]  相似文献   
5.
The effects of temperature, dose rate, and monomer concentration on the heterogeneous polymerization of acrylamide in acetone–water mixtures have been studied. Heterogeneous polymerization takes place in mixtures containing less than 60 vol-% water. The polymerization is steady in acetone and nonsteady in acetone an nonsteady in mixtures containing 10–50 vol-% water. The average rate of polymerization is highest in mixtures with about 20 vol-% water. Polymer molecular weight increases with the increasing water content in range 0–10 vol-% and does not change in the range of 30–70 vol-% water. For the polymerization in acetone and an acetone–water 60/40 mixture the activation energies are 2.3 and ?1.8 kcal/mole, the dose rate exponents of rate are 0.78 and 0.52, and the monomer concentration exponents of rate are 0.5 and 1.6, respectively. The polymer molecular weight increases with decreasing dose rate, decreasing temperature, and increasing monomer concentration. These results are discussed in connection with the mechanism of heterogeneous polymerization and the solvent effect.  相似文献   
6.
In this report, a simple process for preparing HFC-245fa through the reaction of 1,1,1,3,3-pentachloropropane (PCP) and anhydrous HF via two-step vapor-phase catalytic fluorination is described. The antimony pentafluoride catalyst was supported on inert porous materials to improve the catalytic activity. The resulting process catalyst not only exhibited high catalytic activity and excellent thermo-stability, but also improved the performance of SbF5, in terms of hygroscopicity and corrosion.  相似文献   
7.
Chromanmethanol 2, a chiral intermediate for the synthesis of α-tocopherol 1, is prepared from α-hydroxy aldehyde 5, which is obtained by an asymmetric synthesis in over 95% ee.  相似文献   
8.
Photoluminescence (PL) intermittency characteristics are examined for single quantum dots (QDs) in a CdSe QD sample synthesized at a slow rate at 75 degrees C. Although the PL quantum efficiency was relatively low ( approximately 0.25), we noticed that the PL intensity of single CdSe QDs fluctuated on a subsecond time scale with short-lived "on" and "off" states. The subsecond PL intensity fluctuations of CdSe QDs are different from "on" and "off" PL blinking generally observed for QDs fluctuating on a millisecond to minute time scale. We characterized single QDs by identifying polarized excitations, topographic imaging using atomic force microscopy (AFM), and transmission electron microscopy (TEM). From analysis of the PL intensity trajectories from >100 single CdSe QDs, the average intermittency time was 213 ms. From the PL quantum efficiency, slow growth of QDs, intensity trajectory analyses, and previous reports relating surface trap states and PL properties of QDs, we attribute the subsecond PL intensity fluctuations of single CdSe QDs and short-lived "on" and "off" states to a high-density distribution of homogeneous surface trap states.  相似文献   
9.
A novel fluorination reagent and catalyst, SbF5/PAF (porous aluminum fluoride), was prepared by impregnating SbCl5 into PAF and then treating with anhydrous hydrogen fluoride. The prepared reagent had an excellent catalytic activity in halogen-exchange, and also improved the properties of SbF5, such as hydroscopicity, corrosion, and toxicity. SbF5/PAF was successfully used in organic synthesis as a fluorinating reagent, and a fixed bed catalyst for F/Cl exchange.  相似文献   
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