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571.
Nick M. Marinov 《国际化学动力学杂志》1999,31(3):183-220
A detailed chemical kinetic model for ethanol oxidation has been developed and validated against a variety of experimental data sets. Laminar flame speed data (obtained from a constant volume bomb and counterflow twin‐flame), ignition delay data behind a reflected shock wave, and ethanol oxidation product profiles from a jet‐stirred and turbulent flow reactor were used in this computational study. Good agreement was found in modeling of the data sets obtained from the five different experimental systems. The computational results show that high temperature ethanol oxidation exhibits strong sensitivity to the fall‐off kinetics of ethanol decomposition, branching ratio selection for C2H5OH + OH ↔ Products, and reactions involving the hydroperoxyl (HO2) radical. The multichanneled ethanol decomposition process is analyzed by RRKM/Master Equation theory, and the results are compared with those obtained from earlier studies. The ten‐parameter Troe form is used to define the C2H5OH(+M) ↔ CH3 + CH2OH(+M) rate expression as k∞ = 5.94E23 T−1.68 exp(−45880 K/T) (s−1) ko = 2.88E85 T−18.9 exp(−55317 K/T) (cm3/mol/sec) Fcent = 0.5 exp(−T/200 K) + 0.5 exp(−T/890 K) + exp(−4600 K/T) and the C2H5OH(+M) ↔ C2H4 + H2O(+M) rate expression as k∞ = 2.79E13 T0.09 exp(−33284 K/T) (s−1) ko = 2.57E83 T−18.85 exp(−43509 K/T) (cm3/mol/sec) F cent = 0.3 exp(−T/350 K) + 0.7 exp(−T/800 K) + exp(−3800 K/T) with an applied energy transfer per collision value of <ΔEdown> = 500 cm−1. An empirical branching ratio estimation procedure is presented which determines the temperature dependent branching ratios of the three distinct sites of hydrogen abstraction from ethanol. The calculated branching ratios for C2H5OH + OH, C2H5OH + O, C2H5OH + H, and C2H5OH + CH3 are compared to experimental data. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 183–220, 1999 相似文献
572.
N. P. Boley 《Accreditation and quality assurance》1999,4(8):347-349
Proficiency testing (PT) is being increasingly used as an important quality assurance tool for laboratories. The subject
of quality of the providers of PT schemes has been discussed increasingly in recent years. Some countries have implemented
systems for the accreditation of PT schemes. This paper looks at the background to the accreditation of PT schemes, the likely
mechanisms which could be employed for accreditation, and some of the practical aspects. 相似文献
573.
K.-P. Nick J. Richter V. Helbig 《Journal of Quantitative Spectroscopy & Radiative Transfer》1984,32(1):1-8
The plasma of an argon arc has been investigated by applying the partial LTE model (overpopulation of the ground state) and accounting for different kinetic temperatures of electrons and atoms. The plasma analysis is performed without making use of atomic constants (e.g. transition probabilities) from the literature. The experimental results show that LTE is obtained in the 4mm arc at atmospheric pressure for electron densities above 6×1016cm-3. Below this value, increasing under-population of the excited levels with decreasing arc current can be observed. This deviation from LTE may explain some not understood results from previously published spectroscopic observations of argon plasmas. 相似文献
574.
Nick Serpone 《Research on Chemical Intermediates》1994,20(9):953-992
Heterogeneous Photocatalysis (HP) has been examined and explored as a potentially viable alternative technology to classical “best” technologies in both environmental detoxification and in energy production. Both fundamental and applied investigations have been pursued over the last decade (1983–1993). This novel technology employs illuminated semiconductor materials as photocatalysts such as CdS and TiO2 to produce both reducing and highly oxidizing species on the particle surface, poised to unleash redox reactions in aqueous media some of which are not possible by normal chemical means. Our laboratory has been involved in this area and has made a significant contribution in (i) demonstrating the generality of the techniques to mineralize a large variety of environmental organics to carbon dioxide together with disposing of trace and toxic metals from aqueous media, and in (ii) understanding the events taking place initially when the light photons interact with the photocatalysts and later when the mineralization process proceeds to its pathological conclusion(s). In this paper we briefly review some of the salient features of our work in Heterogeneous Photocatalysis over the last decade. 相似文献
575.
Determination of rhizosphere 13C pulse signals in soil thin sections by laser ablation isotope ratio mass spectrometry 总被引:1,自引:0,他引:1
Bruneau PM Ostle N Davidson DA Grieve IC Fallick AE 《Rapid communications in mass spectrometry : RCM》2002,16(23):2190-2194
In grassland ecosystems, soil animals act as key soil engineers and architects. The diversity of soil animals is also a regulator of ecosystem carbon flow. However, our understanding of the link between soil animals, carbon fluxes and soil physical organisation remains poor. An integrated approach based on soil micromorphology and laser ablation stable isotope ratio mass spectrometry (LA-IRMS) was developed to provide spatially distributed data of pulse-derived (13)C tracer from roots in the soil environment. This paper describes the development and testing of a LA-IRMS (13)C/(12)C analytical method on soil thin sections as a means to determine the fate of root carbon derived from photosynthesis into soil. Results from this work demonstrated (1) that micro-scale delta(13)C (per thousand) analysis could be made on targeted features located within a soil thin section and (2) that LA-IRMS delta(13)C (per thousand) measurements made on samples obtained from (13)CO(2) pulse labelled plant-soil blocks confirmed the presence of recent photosynthates in the rhizosphere (1 and 4 weeks post-pulse). 相似文献
576.
Zhao W Chen C Ma W Zhao J Wang D Hidaka H Serpone N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3292-3299
The titanium dioxide photocatalyst is employed to examine the influence of chemisorbed hexachloroplatinate(IV) anions (PtCl(6) (2-)) on the surface of P-25 TiO(2) particles on the photoinduced conversion of the azo dye Ethyl Orange (EO) in visible light-illuminated Pt(IV)/TiO(2) dispersions. Spin-trap electron spin resonance (ESR) spectral results, measurement of quantities of organoperoxides formed, total organic carbon (TOC) and chemical oxygen demand (COD(Cr)) assays, together with XPS evidence show that the self-sensitized transformation dynamics of the EO dye mediated by Pt(IV)/TiO(2) are much faster than those occurring on naked TiO(2) under otherwise identical conditions of visible light irradiation. X-ray photoelectron spectral data also show that under the experimental conditions used, no Pt(0) formed on the titania particles during visible light irradiation. We propose a reaction mechanism in which the more rapid conversion of EO in the presence of PtCl(6) (2-) is caused principally by photoexcitation of the dye and not by localized excitation of the tetrachloroplatinate(IV)/TiO(2) particles. 相似文献
577.
Gatti C Bertini L Blake NP Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4556-4568
Periodic density functional calculations using pseudopotentials and a local basis set were performed on the type I clathrates A(8)Ga(16)Ge(30) (A=Sr, Ba). Both are known to show promising thermoelectric properties. Ab initio wave functions were analyzed within the framework of the quantum theory of atoms in molecules. This enabled us to analyze both the charge transfer and bonding properties of the clathrate from a rigorous quantum mechanical viewpoint. The Ba and Sr centers were found to be largely ionic (charge: ca. +1.7 e) both in the smaller 20-atom and in the larger 24-atom cages, consistent with a Zintl-phase view of these type I clathrates. The assertion that the Sr atoms in the different cages have similar oxidation states is shown to be consistent with multiwavelength diffraction experiments on Sr(8)Ga(16)Ge(30); while the assertion of ionicity of the Sr center is supported by the observation that the adsorption edge lies close to that previously found in the Sr K-edge XANES spectra of Sr(OH)(2).8 H(2)O. As such, this work contradicts previous experimental and theoretical studies that claim that the guest atoms are neutral. We show that the discrepancy is related to the definitions used for electron transfer. Definitions based on electron displacement (rearrangement) in space, as in previous works, do not account for the variation in shape and volume of the atomic catchment regions upon change in the number and average locations of the particles in the system. Eventually, such definitions lead to underestimation of charge transfer. The large binding energy found in earlier work for Ba and Sr in these materials is found to be consistent with a simple picture of charge transfer from the guest to the frame. Preliminary investigations on a clathrate of perfect stoichiometry appear to rule out any important relationship between the observed increase in the thermoelectric figure of merit with increasing external pressure and host-guest charge transfer. 相似文献
578.
Mylonas M Plakatouras JC Hadjiliadis N 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4152-4160
We studied the interactions of Ni(II) and Cu(II) ions with the synthetic tetrapeptides SHHK- and SAHK-, which were blocked by amidation making them more realistic models of the hydrolysis peptidic products of the hexapeptides models of H2A histone. A combination of potentiometric and spectroscopic techniques (UV/Vis, CD, NMR and EPR) suggested that at pH > 7 both tetrapeptides coordinated equatorially through the imidazole ring of His in position 3, the N-terminal amino group and the two amide nitrogens existing between these groups {NH2, 2N-, NIm} forming 4N square-planar complexes. While in the case of the CuH(-1)L complex with SHHK- a possible axial coordination of the imidazole ring of His in position 2 was suggested, in the case of the analogous NiH(-1)L complex a completely different interaction of the same ring with metal ions was observed. As expected these complexes have the same structures with the hydrolysis products produced from the Ni(II)- or Cu(II)-assisted hydrolysis of previously studied hexapeptide models of the C-terminal of histone H2A, due to their predominance at pH > 7.4. In addition, the competition plots presented herein showed that the synthetic tetrapeptides SHHK- and SAHK- have higher affinity towards Ni(II) and Cu(II) ions than the previously studied hexapeptides, suggesting that metal ions remain bound to the peptidic products during the hydrolysis cleavage. Thus, it can be concluded that the stability of Ni(II) or Cu(II) complexes with the synthetic tetrapeptides and consequently with the real hydrolysis peptidic products is the driving force of the hydrolysis reaction of H2A histone blocked hexapeptide models, presented in previous studies. 相似文献
579.
In separate experiments, hydrocarbon solutions of the 11-cis isomers of retinol and retinal containing catalytic amounts of iodine were irradiated with monochromatic light. Changes in absorbance were followed spectroscopically for each wavelength of light and measured as a function of time. The curve obtained by plotting the change in absorbance (delta A) vs time (t) is a hyperbola, and thus the plot of 1/delta A vs 1/t forms a straight line. The half reaction time, t1/2, was extracted from this equation, giving a value for each wavelength of light. The parameter 1/t1/2 is adjusted to compensate for variation of light quanta from the xenon source, and it is plotted vs wavelength. A response spectrum is obtained that is a Gaussian. The lambda max is 510 nm for retinol and 519 nm for retinal. This shows that in the photoisomerization iodine is the absorbing species and not the carbocation, which absorbs at 589 nm. 相似文献
580.
Rachael Padman Glenn J. White Robert Barker Dennis Bly Nick Johnson Hugh Gibson Matt Griffin J. Anthony Murphy Richard Prestage John Rogers et al. 《International Journal of Infrared and Millimeter Waves》1992,13(10):1487-1513
A dual-polarization InSb hot-electron bolometer-mixer receiver has been built for the James Clerk Maxwell Telescope, for operation at 461 and 492 GHz (the frequencies of theJ=43 rotational transition of CO and of the3
P
13
P
0 transition of neutral carbon). Receiver noise temperatures of 500K have been obtained at 461 GHz, in observing bandwidths of 3 MHz. The receiver was designed as a common-user or facility instrument. Here we describe those aspects of the design and construction which enabled this goal to be realized. 相似文献