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1.
2.
The kinetics of the anion-induced (5 × 20) → (1 × 1) surface structural transition of reconstructed Au(100) electrodes was studied in sulfate-containing solutions by current transients. It is shown that lifting of the reconstruction follows a nucleation-and-growth type behavior which can be described by the Avrami equation. Moreover, for high positive potentials, i.e., high anion coverages, the current-transient analysis reveals instantaneous nucleation, whereas for low transition overpotentials and long transition times a mechanism with constant transition rate prevails. Apparent activation energies, which depend strongly on the electrode potential, are derived from the temperature dependence of the Avrami plots. 相似文献
3.
A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc. 相似文献
4.
Cynthia Kolb Whitney 《Foundations of Physics》2007,37(4-5):788-812
This paper revisits the historical sequence in which some of the major developments of 20th-century physics occurred, and
explores how theories could have turned out differently, if the sequence of developments had been different. It shows how
a delay in founding special relativity theory until after (1) at least one puzzling problem in electromagnetic theory could
be acknowledged, and (2) sat least some of the experimental observations pertinent to the development of quantum mechanics
had become well known, could have resulted in a larger theory that covers both domains in a manner quite different from that
of any of the theories we use today. The revised theory dispenses with a separate postulate introducing Planck’s constant
h, identifying instead a physical mechanism that implies the constant. Some important aspects of quantum chemistry then follow.
Editor, Galilean Electrodynamics, Proceedings of the Natural Philosophy Alliance; Visiting Industry Professor, Tufts University,
retired 相似文献
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8.
H.-J. Düssel A. Recca J. Kolb D.O. Hummel J.K. Stille 《Journal of Analytical and Applied Pyrolysis》1982,3(4):307-325
Pyrolysis—field ionization mass spectrometry was used for the investigation of the mechanism of the thermal degradation of polymeric heterocycles. Heat-resistant polymers containing aromatic and heterocyclic units such as polyquinolines and polyquinoxalines have a strong tendency to form large condensed systems during pyrolysis, and finally will carbonize. In the course of this process, side-groups (phenyl) and small fragments (NH3, HCN, acetonitrile, acrylonitrile, etc.) are split off. In addition, large heteroatom-containing fragments such as nitriles can be identified. These, together with some fragments that contain the complete heterocyclic ring, are characteristic of the chain building units (“key fragments”). Furthermore, compounds generated by recombination reactions and intramolecular cyclization are constituents of the pyrolysate. 相似文献
9.
Meyers CY Chan-Yu-King R Hua DH Kolb VM Matthews WS Parady TE Horii T Sandrock PB Hou Y Xie S 《The Journal of organic chemistry》2003,68(2):500-511
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes. 相似文献
10.
Tris{[tri(2-methylphenyl)phosphine]gold(I)}-, tris{[tri(2,4,6-trimethylphenyl)phosphine]gold(I)}- and tris{[tri(cyclohexyl)phosphine]gold(I)}-oxonium tetra-fluoroborate ( 1?3 ) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with 1, t -butylamine tBuNH2 and aniline PhNH2 are readily converted into the tri nuclear imino complexes {[(2-MeC6H4)3P]Au}3NtBu+BF4? ( 4 ) and {[(2-MeC6H4)3P]Au}3NPh+BF ( 5 ) in high yields. With 3 , both aniline and 8-amino-quinoline also give the tri nuclear complexes, i.e. {[(c-C6H11)3P]Au}3 NPh+BF ( 6 ) and {[(c-C6H11)3P]Au}3N(C9H6N)+BF ( 7 ). Auration of aniline with the most sterically hindered reagent 2 yields only the bi nuclear complex {[2,4,6-Me3C6H2)3P] · Au}2N(Ph)H+BF ( 8 ). The reagents 1?3 and the Products 4 – 8 have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds 4 and 6 have been determined by single crystal x-ray diffraction. In the cations of 4 , a triangle of gold atoms with short Au — Au contacts [3.036(1), 3.107(1), and 3.214(1) Å] forms a steep pyramid with the nitrogen atom, in which the angles Au? N? Au are all much smaller than the tetrahedral standard of 109.7°: 94.8(4), 98.1(4), and 103.0(4)°. This triangular Au3 unit is staggered relative to the three methyl groups of the tBu substituent at nitrogen. The results for 6 are similar [Au — Au: 3.037(1), 3.071(1), and 3.222(1) Å; Au? N? Au: 95.3(3), 96.5(3), and 103.6(3)°]. Variable temperature NMR studies of compounds 3 and 8 show hindered rotation of the mesityl groups about the P? C bonds of the ligands originating from the steric congestion within each tertiary phosphine. 相似文献