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71.
Many rate constants, particularly for radical-radical reactions, are determined in systems exhibiting complex kinetics. Parameters often comprise several species concentrations, absorption cross sections, and rate constants. They cannot be obtained from an exact analytic expression, and therefore, must be solved iteratively through an efficient numerical differential equation solver. We examine here the reaction kinetics of the CH3 and the C2H3 mixed-radical system, generated by excimer laser photolysis of methyl vinyl ketone (MVK) at 193.3 nm. As a model, a detailed error analysis for determination of the cross-radical reaction rate constant, the initial CH3 and C2H3 radical concentrations are performed using a least-squares modeling program (Acufit). The least-squares program, an assumed mechanism, a detailed set of signal-averaged data, are viewed as the measuring “instrument.” The output of the “instrument” consists of a “signal” that is fit to the data using the least-squares criterion. This gives estimated parameters that are examined with respect to random as well as systematic errors. The biases due to uncertainties of each known parameter and combined uncertainties on the measured parameters are assessed. © 1994 John Wiley & Sons, Inc. 1 This article is a US Government work and, as such, is in the public domain in the United States of America. 相似文献
72.
Rate constants for the removal of Cl atoms in the reaction Cl + O3 → ClO + O2 were measured by the flash photolysis resonance fluorescence technique over the temperature range 213–298 K. The rate constant is given by the Arrhenius expression (2.94 ± 0.49) × 10?11 exp[?(298 ± 39)/T] in units of cm3 molecule?1 s?1. Comparison with recent results from other laboratories are presented. 相似文献
73.
Zusammenfassung Es wird ein einfaches Verfahren zur Dünnschichtchromatographie von Phenol sowie isomeren Kresolen und Xylenolen auf formamidimprägnierten Kieselgel-G-Platten beschrieben. Die Methode läßt sich direkt auf die Analyse solcher Weichmacher anwenden, bei deren Verseifung Phenole entstehen.
Summary The separation and identification of phenol and the isomeric cresols and xylenols by thin-layer chromatography on silica gel plates impregnated with formamide is described. The method is applicable to the direct analysis of phenols from saponificated plasticizers.相似文献
74.
A continuous gradient elution method for capillary column (less than 0.32 mm I.D.) liquid chromatography was developed. Gradient eluent from a microbore liquid chromatograph was split ahead of the injector so that an accurate percentage (2-3%) of the mobile phase delivered by the pump flowed through the capillary column. The outlet of the column was connected to a length of 0.075 mm I.D. fused-silica capillary tubing which, in turn, was connected to a 6-mm optical path length longitudinal capillary flow cell. Fused-silica capillary columns of 0.32 mm I.D. were slurry-packed efficiently with 7-microns spherical, 300 A pore size, C8 bonded-phase particles, and evaluated in terms of their ability to resolve mixtures of proteins, peptides or phenylthiohydantoin (PTH)-amino acid derivatives. The gradient elution profiles agreed with those obtained using microbore (less than 2.1 mm I.D.) and larger bore columns. The minimum detectable amounts for proteins and PTH-amino acids on 0.32 mm I.D. capillary columns were 50 pg and 25 fmol, respectively. At a flow-rate of 3.6 microliters/min, proteins and peptides were recovered from the capillary columns in volumes of about 2-8 microliters. The use of a multiple-wavelength, forward-optics detector for identifying tryptophan- and tyrosine-containing peptides is discussed. 相似文献
75.
76.
The infrared laser induced decomposition of mixtures of ethyl acetate and isopropyl bromide has been studied. The ratio of the yields of products ethylene and propylene, arising from the unimolecular decomposition reactions: ethyl acetate → ethylene + acetic acid, and isopropyl bromide → propylene + hydrogen bromide, were measured as a function of the ratio of ethyl acetate to isopropyl bromide and pressure of added helium. The results indicate clearly that in these systems non-equilibrium behavior is found up to the highest pressures used (about one atmosphere). A two level kinetic model is suggested which qualitatively explains the observations. 相似文献
77.
The synthesis of a novel motif for threonine protease inhibition is described. The desired E-1,2-dichlorovinyl ethers are obtained from alcohols and trichloroethylene as single diastereomers. Aqueous treatment at pH 11 unmasks the hidden α-chloroacetate, which is required for the reaction with the active site of the protease. 相似文献
78.
The azavinylidene osmium complex [(mes)Os(=N=CPh2(PiPr3)]PF6 (3; MES = 1.3.5-C6H3Me3), which was prepared in two steps from [(mes)OsCl2(PiPr3], CH3CO2Na/KPF6 and HN=CPh2, has been shown to react with trifluoracetic acid to give the isomeric heterocycle [(mes)
6H4)(Pi Pr3)]PF6 (4) in almost quantitative yield. With CF3CO2D, the monodeuterated compound 4-d4,containing a N---D unit in the five-membered ring, is obtained. An analogue of 4 with the composition [(mes)
6H4)(PMe3)]X(X = PF6 14a, SbF6 14b) has been made both from [(mes)Os(=N=CPh2)(PMe3)]PF6 12 and CF3CO2H and from [(mes)OsCl(NH= CPh2(PMe3)]SbF6 (13) and CF3CO2Ag. The reaction of 4 with NaH or KOtBu gives the uncharged heterocycle [(mes)
6 H4)(PiPr3)] (15), while treatment of [(mes)OsCl 2(NH=CPh2)] (19) with NaStBu gives the related complex [(mes)
6H4)(St Bu)] (20). The crystal structure of 4 has been determined. kw]Osmium; Azavinylidene; Cyclometallation; Crystal structure; Arene complexes 相似文献
79.
The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the [110] facets only in the NR, which have higher surface energy. 相似文献
80.