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151.
Alexander I. Titkov Alexey N. Salanov Segrey V. Koscheev Andrey I. Boronin 《Reaction Kinetics and Catalysis Letters》2005,86(2):371-379
Summary The interaction of O2with Pd(110) has been studied by TDS and XPS at T = 400 K and at pressures PO2 from 2.6x10-6to 10 Pa. At low exposures in O2(e£1-5 L), an adsorption layer withqof ca.0.5 and with the O1s peak at BE = 529.3 eV has been found to form on the surface. Whenegrows from 5 to 108L, the position and intensity of the oxygen O1s peak remain practically constant. At the same time, as much as 5 mL of oxygen
is absorbed according to the TDS data. The results obtained by TDS and XPS indicate that oxygen penetrates deep into the subsurface
layers of palladium (315-20 ?) and is distributed in its bulk in a low concentration. 相似文献
152.
用环形扩散管和滤纸联用采样技术采集空气中氨和铵盐 总被引:1,自引:0,他引:1
建立了环形扩散管和滤纸采样夹联用,分形态同时采集空气中所态氨和颗粒态铵盐的方法。在同一气流中,采用涂渍1.5%草酸乙醇水溶液的环形扩散管采集气态氨,用浸渍上述试剂的玻璃纤维纸和慢速定量滤纸分别采集颗粒安和第一层滤纸上的铵盐挥发产生的氨气。用靛酚蓝比色法分别测定氨和铵盐。当采气流速为1.0L/min时,采样效率高于98.2%。将本法测得的氨气和铵盐的总量与标准采样方法的测定结果比较。无显著性差异(P 相似文献
153.
Tin dioxide SnO2−δ is a pronounced n-type electron conductor due to its oxygen deficiency. This study investigates the rate of chemical diffusion of oxygen in SnO2−δ single crystals, which is a crucial step in the overall stoichiometry change of the material. The chemical diffusion coefficient Dδ was determined from conductivity- and EPR-relaxation methods. The temperature dependence was found to be . The dependence on crystal orientation, dopant content and oxygen partial pressure was below experimental error. The latter observation leads to the conclusion that the chemical diffusion coefficient is close to the diffusion coefficient of oxygen vacancies. Along with the relaxation process resulting from the chemical diffusion of oxygen, additional processes were observed. One of these was attributed to complications in the defect chemistry of the material. The relevance of the results for the kinetics of drift processes of Taguchi sensors is discussed. 相似文献
154.
Shlomo Havlin James E. Kiefer George H. Weiss Daniel Benavraham Yehoshua Glazer 《Journal of statistical physics》1985,41(3-4):489-496
We discuss and analyze a family of trees grown on a Cayley tree, that allows for a variable exponent in the expression for the mass as a function of chemical distance, M(l)l
dl
. For the suggested model, the corresponding exponent for the mass of the skeleton,d
l
s
, can be expressed in terms ofd
l
asd
l
s
= 1,d
l
d
l
c
= 2;d
l
s
= d
l
–1,d
1
d
l
c
= 2, which implies that the tree is finitely ramified ford
l
2 and infinitely ramified whend
l
2. Our results are derived using a recursion relation that takes advantage of the one-dimensional nature of the problem. We also present results for the diffusion exponents and probability of return to the origin of a random walk on these trees. 相似文献
155.
用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H2S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H2S反应,生成含PbS纳米微粒的凝胶;但其体积增大不同,这说明H2S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。 相似文献
156.
157.
V. Lj. Marković M. M. Pejović Z. Lj. Petrović 《Plasma Chemistry and Plasma Processing》1996,16(2):195-208
The late afterglow in nitrogen with iron electrode is studied by the breakdown time delay method, i.e., by measuring the breakdown time delay td as a function of the afterglow time . It is proposed that the cause of the secondary electrons initiating the breakdown is the energy of the surface recombination of nitrogen atoms on the iron electrode. The gas-phase and macrokinetic diffusive models are used to describe the experimental breakdown time delay data. By fitting the theoretical curve to the experimental data: (1) it has been confirmed that the recombination on the molybdenum glass is of the second order and the value of the surface recombination coefficient is determined at 4 mbar; (2) it has been shown that the surface recombination on the iron electrode is of the second order, and the effective recombination coefficients are determined; (3) the analytical form of the recombination coefficient as a function of the adsorption characteristics of surfaces and the pressure of the parent gas has been derived. In addition, the orders of surface recombination on the molybdenum-, aluminum-, and gold-plated electrode were determined by the same method. 相似文献
158.
A relationship is derived to enable the comparison of the dispersion heights of normal and reverse flow injection analysis (FIA). A single channel flow system is employed in the absence of a chemical reaction. The stopped-flow injection method is used to probe the influence of molecular diffusion on the overall dispersion of normal and reverse FIA, which appeared to demonstrate fundamentally different diffusion behaviors. Small discrepancies are observed between the dispersion heights, which are enhanced by the stopped-flow period, especially when unmatched matrix ionic compositions of the indicator and counter solutions were involved. For these conditions, the diffusion flux rate is enhanced considerably, displaying a peak, in addition to the transient, for both methods. The influence of diffusion on the dispersion characteristics of normal and reverse FIA is discussed theoretically. Diffusion in the proposed model is postulated to oppose dispersion by convection. The latter initiates concentration gradients in the injection zone and propagates it with flow time over the dispersion zone profile. The diffusion flux then reacts in order to confine the indicator dispersion for normal FIA and to enhance it for reverse FIA. This model is consistent with the experimental results and accounts for most of the phenomena encountered. Probably owing to the influence of secondary flow phenomena, the use of coiled tubes has suppressed the effects of diffusion on the overall dispersion behavior.Part of the experimental work was performed at IMI Institute for Research and Development, Haifa, Israel. 相似文献
159.
Hayley A. Every Michael A. Hickner James E. McGrath Thomas A. Zawodzinski Jr. 《Journal of membrane science》2005,250(1-2):183-188
Methanol diffusion in two polymer electrolyte membranes, Nafion 117 and BPSH 40 (a 40% disulfonated wholly aromatic polyarylene ether sulfone), was measured using a modified pulsed field gradient NMR method. This method allowed for the diffusion coefficient of methanol within the membrane to be determined while immersed in a methanol solution of known concentration. A second set of gradient pulses suppressed the signal from the solvent in solution, thus allowing the methanol within the membrane to be monitored unambiguously. Over a methanol concentration range of 0.5–8 M, methanol diffusion coefficients in Nafion 117 were found to increase from 2.9 × 10−6 to 4.0 × 10−6 cm2 s−1. For BPSH 40, the diffusion coefficient dropped significantly over the same concentration range, from 7.7 × 10−6 to 2.5 × 10−6cm2 s−1. The difference in diffusion behavior is largely related to the amount of solvent sorbed by the membranes. Increasing the methanol concentration results in an increase in solvent uptake for Nafion 117, while BPSH 40 actually excludes the solvent at higher concentrations. In contrast, diffusion of methanol measured via permeability measurements (assuming a partition coefficient of 1) was lower (1.3 × 10−6 and 6.4 × 10−7 cm2 s−1 for Nafion 117 and BPSH 40 respectively) and showed no concentration dependence. The differences observed between the two techniques are related to the length scale over which diffusion is monitored and the partition coefficient, or solubility, of methanol in the membranes as a function of concentration. For the permeability measurements, this length is equal to the thickness of the membrane (178 and 132 μm for Nafion 117 and BPSH 40 respectively) whereas the NMR method observes diffusion over a length of approximately 4–8 μm. Regardless of the measurement technique, BPSH 40 is a greater barrier to methanol permeability at high methanol concentrations. 相似文献
160.
Kinetic parameters of interphase exchange of oxygen in high-temperature proton conductors BaCe0.95Nd0.05O3- and SrCe0.95Y0.05O3- are determined using an isotope exchange method in the temperature range 630-820°C at oxygen pressures of 2.7-13.3 gPa and diffusion coefficients for oxygen are calculated. Effective energies of activation of oxygen exchange and diffusion coefficients for oxygen are calculated. Dependence of exchange characteristics and the diffusion coefficients on the oxygen pressure in the gas phase is investigated. The oxygen exchange on the surface of studied oxides is shown to proceed only with the participation of oxygen of the oxides, which causes high rates of interphase exchange of oxygen of studied cerates of barium and strontium. It is shown that the obtained data satisfactorily agree with those found in the relevant literature. 相似文献