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41.
Measured CH and C2 profiles show a striking resemblance as a function of time in a series of seven well-characterized fuel-rich (phi=1.2-2.0) non-sooting acetylene flames. This implied commonality and interrelationship are unexpected as these radicals have dissimilar chemical kinetic natures. As a result, a rigorous examination was undertaken of the behavior of each of the hydrocarbon species known to be present, C, CH, CH2, CH3, CH4, CHO, CHOH, CH2O, CH2OH, CH3O, CH3OH, C2, C2H, C2H2, CHCO, CH2CO, and C2O. This emphasized the main region where CH and C2 are observed (50-600 micros) and reduced the kinetic reactions to only those that operate efficiently and are dominant. It was immediately apparent that this region of the flame reflects the nature of a hydrogen flame heavily doped with CO and CO2 and containing traces of hydrocarbons. The radical species, H, OH, O, along with H2, H2O, and O2, form an important controlling radical pool that is in partial equilibrium, and the concentrations of each of the hydrocarbon radicals are minor to this, playing secondary roles. As a result, the dominant fast reactions are those between the hydrocarbons and the basic hydrogen/oxygen radicals. Hydrocarbon-hydrocarbon reactions are unimportant here at these equivalence ratios. CH and C2 are formed and destroyed on a sub-microsecond time scale so that their flame profiles are the reflection of a complex kinetically dynamic system. This is found to be the case for all of the hydrocarbon species examined. As might be expected, these rapidly form steady-state distributions. However, with the exceptions of C, CHO, CHOH, and CH2O, which are irreversibly being oxidized, the others all form an interconnected hydrocarbon pool that is under the control of the larger hydrogen radical pool. The hydrocarbon pool can rapidly adjust, and the CH and C2 decay together as the pool is drained. This is either by continuing oxidation in less rich mixtures, or in richer flames where this is negligible by the onset of hydrocarbon-hydrocarbon reactions. The implications of such a hydrocarbon pool are significant. It introduces a buffering effect on their distribution and provides the indirect connection between CH and C2. Moreover, because they are members of this radical pool, flame studies alone cannot answer questions concerning their specific importance in combustion other than their contributing role to this pool. The presence of such a pool modifies the exactness that is needed for kinetic mechanisms, and knowledge of every species in the system no longer is necessary. Furthermore, as rate constants become refined, it will allow for the calculation of the relative concentrations of the hydrocarbon species and facilitate reduced kinetic mechanisms. It provides an explanation for previous isotopically labeled experiments and illustrates the difficulty of exactly identifying in flames the role of individual species. It resolves the fact that differing kinetic models can show similar levels of accuracy and has implications for sensitivity analyses. It finally unveils the mechanism of the flame ionization detector and has implications for the differing interpretations of diamond formation mechanisms. 相似文献
42.
Mimicking a Stenocara beetle's back for microcondensation using plasmachemical patterned superhydrophobic-superhydrophilic surfaces 总被引:1,自引:0,他引:1
Garrod RP Harris LG Schofield WC McGettrick J Ward LJ Teare DO Badyal JP 《Langmuir : the ACS journal of surfaces and colloids》2007,23(2):689-693
A simple two-step plasmachemical methodology is outlined for the fabrication of microcondensor surfaces. This comprises the creation of a superhydrophobic background followed by pulsed plasma deposition of a hydrophilic polymer array. Microcondensation efficiency has been explored in terms of the chemical nature of the hydrophilic pixels and their dimensions. These results are compared to the hydrophilic-hydrophobic pattern present on the Stenocara beetle's back, which is used by the insect to collect water in the desert. Potential applications include fog harvesting, microfluidics, and biomolecule immobilization. 相似文献
43.
Bradley TJ Schofield WC Garrod RP Badyal JP 《Langmuir : the ACS journal of surfaces and colloids》2006,22(18):7552-7555
Pulsed plasma-chemical deposition of poly(4-vinylpyridine) is found to be a highly effective way of functionalizing solid surfaces with pyridine ring centers. These surfaces can be metallized via complexation to Pd2+ ions from solution, followed by autocatalytic electroless deposition of either copper or nickel films. 相似文献
44.
Schofield MH Sorel MA Manalansan RJ Richardson DP Markgraf JH 《Magnetic resonance in chemistry : MRC》2006,44(9):851-855
The synthesis and assignment of 15N and 13C NMR signals of the isoxazole ring in a series of para-substituted 3-phenyl derivatives are reported. DFT calculations of 15N and 13C chemical shifts are presented and compared to observed values. Substituent effects are interpreted in terms of the Hammett correlation and calculated bond orders. 相似文献
45.
Bassan A Borowski T Schofield CJ Siegbahn PE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(34):8835-8846
The reaction catalyzed by the plant enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) was investigated by using hybrid density functional theory. ACCO belongs to the non-heme iron(II) enzyme superfamily and carries out the bicarbonate-dependent two-electron oxidation of its substrate ACC (1-aminocyclopropane-1-carboxylic acid) concomitant with the reduction of dioxygen and oxidation of a reducing agent probably ascorbate. The reaction gives ethylene, CO(2), cyanide and two water molecules. A model including the mononuclear iron complex with ACC in the first coordination sphere was used to study the details of O-O bond cleavage and cyclopropane ring opening. Calculations imply that this unusual and complex reaction is triggered by a hydrogen atom abstraction step generating a radical on the amino nitrogen of ACC. Subsequently, cyclopropane ring opening followed by O-O bond heterolysis leads to a very reactive iron(IV)-oxo intermediate, which decomposes to ethylene and cyanoformate with very low energy barriers. The reaction is assisted by bicarbonate located in the second coordination sphere of the metal. 相似文献
46.
Crawford TD Abrams ML King RA Lane JR Schofield DP Kjaergaard HG 《The Journal of chemical physics》2006,125(20):204302
Vertical and adiabatic excitation energies of the lowest (2)A(') excited state in the water-hydroxyl complex have been determined using coupled cluster, multireference configuration interaction, multireference perturbation theory, and density-functional methods. A significant redshift of about 0.4 eV in the vertical excitation energy of the complex compared to that of the hydroxyl radical monomer is found with the coupled cluster calculations validating previous results. Electronic excitation leads to a structure with near-equal sharing of the hydroxyl hydrogen by both oxygen atoms and a concomitantly large redshift of the adiabatic excitation energy of approximately 1 eV relative to the vertical excitation energy. The combination of redshifts ensures that the electronic transition in the complex lies well outside the equivalent excitation in the hydroxyl radical monomer. The complex is approximately five times more strongly bound in the excited state than in the ground state. 相似文献
47.
Schofield K 《The journal of physical chemistry. A》2006,110(21):6938-6947
Although the "Golden" years of spectroscopy and the major studies on ionization processes now are behind us, as with many branches of science, much yet remains to be gleaned from such topics that is both full of interest and of significance to present day research. Presented here is one such overlooked example, an observation that relates to both these fields. An analysis is presented for the periodic table concerning the gas-phase thermochemical nature of MO+ and MO2+ ions. Unexpectedly, a pattern of 18 elements has been identified that exhibit the potential for having long-lived MO+ ions. Normally such molecular ions are expected to decay extremely rapidly by dissociative recombination with electrons, but in particular, 12 of this group behave not like molecules but rather as atomic ions. These are the diatomic oxide ions of Sc, Y, La, Zr, Hf, Ce, Pr, Nd, Pm, Gd, Tb, and Th. In the gas phase, they decay by much slower three-body recombination channels. As may be noted, these elements are located in the first two columns of the transition elements, among the earlier rare earths and an actinide. From all the elements, UO2+ is the only dioxide ion that behaves similarly. These findings now elevate the potential importance of these ions and should facilitate their spectral characterization. Moreover, subsequent comparisons with spectra of well-known isoelectronic and isovalent neutral monoxides and other diatomics will help in the stimulation of further theoretical advances. In addition, once characterized, an ease of spectrally monitoring such ionic states will provide a useful analytical tool. 相似文献
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In disordered colloidal systems, we experimentally measure the normal modes with the covariance matrix method and clarify the origin of low-frequency quasilocalization at the single-particle level. We observe important features from both jamming and glass simulations: There is a plateau in the density of states [D(ω)] which is suppressed upon compression, as predicted by jamming; within the same systems, we also find that the low-frequency quasilocalization originates from the large vibrations of defective structures coupled with transverse excitations, consistent with a recent glass simulation. The coexistence of these features demonstrates an experimental link between jamming and glass. Extensive simulations further show that such a structural origin of quasilocalization is universally valid for various temperatures and volume fractions. 相似文献