Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (3–)+H2 (1g+
) NH2 (2B1)+H (2S) involving the lowest triplet electronic state of NH3 were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol–1 agrees with the experimental value within 2 kcal mol–1. The barrier to reaction is 23.4 kcal mol–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H2, whereas those of the reverse reaction are by a factor of 20 larger than those of OH2 with H. 相似文献
Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a
useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed
in the pores. Measurements of the surface area (BET, N2) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles
with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of
PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the
pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
A preconcentration procedure was established for sulphate determination in rain waters at the mg/l level, employing a small column packed with the AG1-X8 (200-400 mesh) anionic resin inserted into a flow injection system. Sulphate determination was performed by using the turbidimetric method based on reaction with barium. For concentrations within 0.10 and 2.0 MgSO(2-)(4)/l, a throughput of 50 determinations/hr was achieved, and the relative standard deviation of results was better than 2%. 相似文献
The photochemical CO-loss products of the diruthenium complexes [CpRu(CO) 2]2 (5; Cp = 5-C5H5), [Cp*Ru(CO)2]2 (5*; Cp* = 5-C5(CH3)5) and CpCp*[Ru(CO)2]2 (5) have been studied experimentally in low-temperature (96 K) matrices in 3-methylpentane by using IR spectroscopy. It is proposed that all three complexes undergo single-CO-loss chemistry but that the products have different structures. The single-CO-loss product from 5 is proposed to have one bridging and two terminal carbonyl ligands, whereas 5* and 5 generate triply bridged CO-loss products similar to that observed from [CpFe(CO)2]2 and [Cp*Fe(CO)2]2. Double-CO-loss from 5* and 5*9 is also apparently observed. Relativistic DFT calculations have been carried out on various isomers of the starting materials and on potential CO-loss products from 5. The calculations suggest that the triply bridged product Cp2Ru2(-CO)3 (6) might have a singlet ground state in contrast to the corresponding diiron complex Cp2Fe2(-CO)3 (3), which has a triplet ground state. 相似文献
By the use of TG—MS, the thermal dissociation of anhydrous CuSO4 and Al2(S04)3 was found to proceed according to the reactions: followed by the reactions: No SO3 was indicated in the dissociation of alunite. The sulfate ion appears to dissociate by at least two different mechanisms although the parameter which controls the mechanisms has not been elucidated. 相似文献
Surface acoustic waves (SAW), or Rayleigh waves, bound to the surfaces of piezoelectric materials are becoming rapidly significant in electronic device applications, particularly as VHF-UHF frequency filters and versatile time-domain processors. The majority of available devices utilize either signle crystalline quartz or lithium niobate as the piezoelectric medium. This paper describes briefly the growth and critical evaluation of SAW impedance and propagation properties for certain new single crystal piezoelectric materials. Crystals discussed are Czochralski-grown bismuth germanium oxide, films of zinc oxide and aluminum nitride both epitaxially grown on single crystal sapphire, and flux-grown beryllium oxide. It is concluded that bismuth germanium oxide may prove an important cost-effective alternative to both quartz and lithium niobate, and that either zinc oxide or aluminum nitride is destined to prove invaluable in the realization of monolithic circuits such as programmable tapped delay lines, in which SAW will be interfaced with metal-oxide semiconductor (large scale integrated) technology, and active SAW elements employing functional integration. 相似文献
Human investigators instinctively segment medical images into their anatomical components, drawing upon prior knowledge of anatomy to overcome image artifacts, noise, and lack of tissue contrast. The authors describe: 1) the development and use of a brain tissue probability model for the segmentation of multiple sclerosis (MS) lesions in magnetic resonance (MR) brain images, and 2) an empirical comparison of the performance of statistical and decision tree classifiers, applied to MS lesion segmentation. Based on MR image data obtained from healthy volunteers, the model provides prior probabilities of brain tissue distribution per unit voxel in a standardized 3-D "brain space". In comparison to purely data-driven segmentation, the use of the model to guide the segmentation of MS lesions reduced the volume of false positive lesions by 50-80% 相似文献