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971.
Description of the response of a fiber optic velocity sensor applied to capillary gas chromatography
This paper explores the response of a novel fiber optics sensor allowing real-time determination of the migration rate of vapor zones in capillary gas chromatography. The sensitivity is related to the gradient of the vapor zone distribution in the capillary and it is highest when vapor zones show steep variations in concentration. The expected linearity between the height of the velocity peaks and the response of a thermal conductivity detector is demonstrated experimentally. The sensor can be used to infer an approximate value of the analyte diffusion coefficient from the time response. Finally, the time evolution of the envelope of the optical signal is explained with experimental evidences. 相似文献
972.
Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria. 相似文献
973.
Yue Zhang Tianlei Zhang Wenliang Wang 《International journal of quantum chemistry》2011,111(12):3029-3039
A theoretical study of the mechanism and the kinetics for the hydrogen abstraction reaction of the biradical hydroperoxy radical has been presented at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) level of theory. Our theoretical calculations suppose a stepwise mechanism involving the formation of a postreactant complex in the triplet and singlet entrance channels. Four transition states of the six‐membered chain complexes (3TS1 and 1TS1) and six‐membered ring complexes (3TS2 and 1TS2) are located at the high dual level CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) method. The rate constants of Path 1 ~ Path 4 at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G (d,p) level are calculated by means of the conventional transition state theory (TST) and canonical variational TST without and with small‐curvature tunneling (SCT) correction within the temperature range of 200–2,500 K. The calculated results show that the triplet channel is the dominating reaction channel and Path 2 is found to be the most favorable pathway. The rate constants of Path 2 are in good agreement with the experimental values at the experimentally measured temperatures. Moreover, the variational effect is not obvious in the low temperature range but is not neglectable in the high temperature range. The SCT plays an important role particularly in the low temperature range. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
974.
Zhang G Jin Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(5):1567-1571
The electronic quenching rate constants of NO A(2)Σ (υ'=0, 1), E(2)Σ (υ'=2, 3, 4) and F(2)Δ (υ'=1, 2, 3) states by gas air are reported. The experiments were carried out by measuring the total fluorescence intensity of A(2)Σ (υ'=0, 1)→X(2)Π (υ″) transition at various air pressures. It gives the Stern-Volmer plots. The quenching rate constants of A(2)Σ (υ'=0, 1) states are obtained from the slope of Stern-Volmer plots and the known radiative lifetime. Based on the primary results of the work, we have measured the quenching rate constants of high excited E(2)Σ (υ'=2, 3, 4), F(2)Δ (υ'=1, 2, 3) states for the first time with the technique of photo-acoustic (PA) spectroscopy. It is shown that the electronic quenching rate constants of NO E (υ') and F (υ') states are in the order of 10(-10)cm(3)/molecules. They are much larger than those of A(2)Σ (υ') state, whose rate constants are in the order of 10(-13)cm(3)/molecules. For E (υ') and F (υ') states, it is also found that the quenching rate constants increase with the vibrational energy levels. Similar result has been reported also for A(2)Σ (υ'≥2) states in existing literatures. The agreement indicates the potential use of PA spectroscopy for measuring the electronic quenching rate. 相似文献
975.
976.
G.C. Sih 《Theoretical and Applied Fracture Mechanics》2011,55(1):52-59
The energy release rate criterion, being mono scale by definition, is incompatible with the failure behavior of solids that are inherently dual, if not, multiscale. Time span of reliability is scale sensitive and can be addressed with consistency only by use of transitional functions that are designed to transform a function from one scale to another. A pseudo transitional energy release rate G∗ is defined to address the cross-scaling properties of energy release rate. The reliability of such a function is found to fall quickly when the scale range deviates from that of micro-macro. In general, the time span of reliability based on G* shortens considerably within the nano-micro and pico-nano scale ranges, resulting in fast turnover of system usability. Prediction accuracy tends to be scale range specific. Stress or strain based criteria are also mono scale. They may be adequate for some situations at the macroscopic scale, but can be ambiguous for multiscale problems. These situations are analyzed by application of the principle of least variance in conjunction with the R-integrals.Accelerated test data for the equivalent of 20 years’ fatigue crack growth in 2024-T3 aluminum panels were analyzed using the mutliscale reliability model. A time span plateau within the micro-macro range is from 8 to 17 years. This corresponds to the reliable portion of prediction, while the terminal 3 years are regarded as unreliable. A similar time span plateau were also found from 4 to 6 years within the nano-micro scale range. And an even smaller plateau hovering around 1.2 years were found for the pico-nano scale range. Time span of reliable prediction narrows with down sized scale range. The overlapping ends of the scale ranges are rendered unreliable as anticipated. These regions can be suppressed by the addition of meso scale ranges. Reference can be made to past discussions related to multiscaling and mesomechanics. 相似文献
977.
The anti-plane problem of an elliptical inhomogeneity with an interfacial crack in piezoelectric materials is investigated. The system is subjected to arbitrary singularity loads (point charge and anti-plane concentrated force) and remote anti-plane mechanical and in-plane electrical loads. Using the complex variable method, the explicit series form solutions for the complex potentials in the matrix and the inclusion regions are derived. The electroelastic field intensity factors, the corresponding energy release rates and the generalized strain energy density at the cracks tips are then provided. The influence of the aspect ratio of the ellipse, the crack geometry and the electromechanical coupling coefficient on the energy release rate and the strain energy density is discussed and shown in graphs. The results indicate that the energy release rate increases with increment of the aspect ratio of the ellipse and the influence of electromechanical coupling coefficient on the energy release rate is significant. The strain energy density decreases with increment of the aspect radio of the ellipse and it is always positive for the cases discussed. The energy release rate, however, can be negative when both mechanical and fields are applied. 相似文献
978.
A new formula is obtained to calculate dynamic stress intensity factors of the three-point bending specimen containing a single edge crack in this study. Firstly, the weight function for three-point bending specimen containing a single edge crack is derived from a general weight function form and two reference stress intensity factors, the coefficients of the weight function are given. Secondly, the history and distribution of dynamic stresses in uncracked three-point bending specimen are derived based on the vibration theory. Finally, the dynamic stress intensity factors equations for three-pointing specimen with a single edge crack subjected to impact loadings are obtained by the weight function method. The obtained formula is verified by the comparison with the numerical results of the finite element method (FEM). Good agreements have been achieved. The law of dynamic stress intensity factors of the three-point bending specimen under impact loadings varing with crack depths and loading rates is studied. 相似文献
979.
Using the complex variable function method and the technique of the conformal mapping, the fracture problem of a semi-infinite crack in a piezoelectric strip is studied under the anti-plane shear stress and the in-plane electric load. The analytic solutions of the field intensity factors and the mechanical strain energy release rate are presented under the assumption that the surface of the crack is electrically impermeable. When the height of the strip tends to infinity, the analytic solutions of an infinitely large piezoelectric solid with a semi-infinite crack are obtained. Moreover, the present results can be reduced to the well-known solutions for a purely elastic material in the absence of the electric loading. In addition, numerical examples are given to show the influences of the loaded crack length, the height of the strip, and the applied mechanical/electric loads on the mechanical strain energy release rate. 相似文献
980.