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Reaction Models (reaction + models)
Selected AbstractsKinetic Reaction Models for the Selective Reduction of NO by Methane over Multifunctional Zeolite-based Redox CatalystsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 12 2004T. Sowade Abstract Kinetic measurements of the selective catalytic reduction (SCR) of NO by methane were performed over CeO2/H-ZSM-5, In-ZSM-5, and CeO2/In-ZSM-5 catalysts. The parameter space covered NO, CH4, and O2 concentrations varying from 250 to 1000 ppm, from 500 to 2000 ppm, and from 0.5 to 10,vol.-%, respectively, space velocities between 5000 and 90000 h,1 and temperatures between 573 and 873 K depending on the catalyst activities. With CeO2/In-ZSM-5 an additional series of measurements was performed with moistened feed gas (0.5,10,vol.-% H2O). On the basis of a pseudo-homogeneous, one-dimensional fixed-bed reactor model, the data were fitted to a kinetic model that includes power rate laws for the reduction of NO and for the unselective total oxidation of methane. From analyses of isothermal data sets, almost all reaction orders were found to vary significantly with changing temperature, which indicates that the simple kinetic model cannot reflect the complex reaction mechanism correctly. Nevertheless, the data measured with In-ZSM-5 could be modeled with good accuracy over a wide range of reaction temperatures (150 K) while the accuracy was less satisfactory with the remaining data sets, in particular for data with the moist feed over CeO2/In-ZSM-5. With the latter catalyst it was not possible to represent the data measured in dry and in moist feed in a single model even upon confinement to fixed reaction temperatures. A comparison of the separate models established showed strong changes in the reaction orders in the presence of water, which occur apparently already at a very low water content (,,0.5,vol.-%). The kinetic parameters found are in agreement with earlier conclusions about the reaction mechanisms. With In-ZSM-5, both reaction orders and the activation energy show a rate-limiting influence of NO oxidation on the NO reduction path which is removed by the presence of the CeO2 promoter. A difference in the reaction mechanism over CeO2/In-ZSM-5 and CeO2/H-ZSM-5 is reflected in different kinetic parameters. The differences of the kinetic parameters between dry-feed and moist-feed models for CeO2/In-ZSM-5 reflect adsorption competition between the reactants and water. [source] Effects of host mineral re-equilibration during uplift and cooling on the fidelity of primary hydrothermal fluid inclusions: a theoretical example using Mississippi Valley-type ore fluidsGEOFLUIDS (ELECTRONIC), Issue 2 2009M. A. McKIBBEN Abstract At the moment of its trapping as a primary fluid inclusion, a hydrothermal fluid is typically at or near equilibrium with multiple mineral species at depth and temperature. After trapping, however, the isolated inclusion fluid can re-equilibrate only with its own host mineral species during later uplift and cooling to surface conditions. Because the solubility versus temperature behavior is unique for each host mineral species, identical inclusions trapped at the same time within different species may re-equilibrate in a disparate manner upon cooling and become variably less representative of the original trapped fluid once they reach ambient temperature. To test the significance of this effect, a series of theoretical equilibrium reaction models was constructed in which a trapped hydrothermal fluid characteristic of Mississippi Valley-type ore deposits is cooled in contact with silicate, sulfide and carbonate hosts, respectively, from 100 to 25°C. Dissolved base metal concentrations are predicted to decline by two to four orders of magnitude in inclusions in all hosts, due to the precipitation of optically undetectable masses of sulfide daughter minerals. Fluids in the calcite host show the greatest decline in dissolved base metals upon cooling, due to its retrograde solubility and consequent shift in the pH and aqueous C speciation of the fluid. ,13C values for CO2 in all hosts become depleted by 2,7, relative to the original trapped fluid, with depletions again being the greatest for the calcite host due to its retrograde dissolution. Analytical techniques that extract and analyze the complete contents of fluid inclusions at room temperature can account for the predicted precipitation of microscopic daughter minerals during cooling, but may not compensate for chemical changes caused by the retrograde dissolution of calcite. Such solubility effects are another reason to be cautious in using carbonate minerals for fluid inclusion studies, in addition to their undesirable physical properties of softness, deformability and perfect cleavage. [source] The transfer matrix method applied to steel sheet pile wallsINTERNATIONAL JOURNAL FOR NUMERICAL AND ANALYTICAL METHODS IN GEOMECHANICS, Issue 6 2003D. A. Kort Abstract This paper proposes two subgrade reaction models for the analysis of steel sheet pile walls based on the transfer matrix method. In the first model a plastic hinge is generated when the maximum moment in the retaining structure is exceeded. The second model deals with a beam with an asymmetrical cross-section that can bend in two directions. In the first part of this paper the transfer matrix method is explained on the basis of a simple example. Further the development of two computer models is described: Plaswall and Skewwall. The second part of this paper deals with an application of both models. In the application of Plaswall the effect of four current earth pressure theories to the subgrade reaction method is compared to a finite element calculation. It is shown that the earth pressure theory is of major importance on the calculation result of a sheet pile wall both with and without a plastic hinge. In the application of Skewwall the effectiveness of structural measures to reduce oblique bending is investigated. The results are compared to a 3D finite element calculation. It is shown that with simple structural measures the loss of structural resistance due to oblique bending can be reduced. Copyright © 2003 John Wiley & Sons, Ltd. [source] Moment independent and variance-based sensitivity analysis with correlations: An application to the stability of a chemical reactorINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2008E. Borgonovo Recent works have attracted interest toward sensitivity measures that use the entire model output distribution, without dependence on any of its particular moments (e.g., variance). However, the computation of moment-independent importance measures in the presence of dependencies among model inputs has not been dealt with yet. This work has two purposes. On the one hand, to introduce moment independent techniques in the analysis of chemical reaction models. On the other hand, to allow their computation in the presence of correlations. To do so, a new approach based on Gibbs sampling is presented that allows the joint estimation of variance-based and moment independent sensitivity measures in the presence of correlations. The application to the stability of a chemical reactor is then discussed, allowing full consideration of historical data that included a correlation coefficient of 0.7 between two of the model parameters. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 687,698, 2008 [source] A new approach to response surface development for detailed gas-phase and surface reaction kinetic model optimizationINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2004Scott G. Davis We propose a new method for constructing kinetic response surfaces used in the development and optimization of gas-phase and surface reaction kinetic models. The method, termed as the sensitivity analysis based (SAB) method, is based on a multivariate Taylor expansion of model response with respect to model parameters, neglecting terms higher than the second order. The expansion coefficients are obtained by a first-order local sensitivity analysis. Tests are made for gas-phase combustion reaction models. The results show that the response surface obtained with the SAB method is as accurate as the factorial design method traditionally used in reaction model optimization. The SAB method, however, presents significant computational savings compared to factorial design. The effect of including the partial and full third order terms was also examined and discussed. The SAB method is applied to optimization of a relatively complex surface reaction mechanism where large uncertainty in rate parameters exists. The example chosen is laser-induced fluorescence signal of OH desorption from a platinum foil in the water/oxygen reaction at low pressures. We introduce an iterative solution mapping and optimization approach for improved accuracy. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 94,106, 2004 [source] Degradation Kinetics of Capsanthin in Paprika (Capsicum annuum L.) as Affected by HeatingJOURNAL OF FOOD SCIENCE, Issue 1 2001J.H. Shin ABSTRACT: Diluted juice of paprika was heated at 80, 90 and 100°C with holding times of 0, 2, 4, 8 and 16 min. Capsanthin in each sample was determined by HPLC. The degradation kinetics of capsanthin was studied by two groups of reaction models including elementary reaction rate models and those of modified square root-based pseudo (MRBP-). The MRBP-1st order reaction rate model was proven as an appropriate model in this study. The pseudo Q10 (PQ10) value was 1.045 and the predicted half-life (capsanthin 2,850 mg/L) was 27.47, 21.23 and 15.23 min, respectively, at 80, 90 and 100°C. [source] Solid-solid reactions in series: A modeling and experimental studyAICHE JOURNAL, Issue 9 2009A. K. Suresh Abstract Reactions among particulate solid phases are important and abundant in many materials, chemical, and metallurgical process industries. Many of these are reaction networks, and not single-step reactions as normally assumed. There is no theoretical framework available for the analysis of such systems, and single-reaction models derived from the gas,solid literature continue to be used. Formation of cement clinker in the rotary cement kiln is a prime example of the genre, in which mechanistic aspects play an important role in determining energy efficiency and the composition and nature of the phases that form. In the present study, we formulate a model within the ambit of the "shrinking core" class of models, for reactions in series among solid phases. The model shows the presence of one or two moving fronts in the reacting particle, depending on the relative rates of the processes involved. A single Thiele-type parameter controls the model behavior, at once describing the relative rates of the intermediate formation and consumption processes, and the diffusion-reaction competition for the product formation step. The model has been shown to reduce to the well known single reaction models at the limits of low and high values of the Thiele parameter. Experimental data have been obtained on the calcia-alumina system, an important one in cement manufacture, in the temperature range 1150,1250°C. The model has been fitted to these data and the kinetic parameters determined. The comparison bears out the salient features of the theory, and shows that a degree of diffusion limitation exists for the intermediate conversion step under these conditions. The diffusivity values estimated are in the range of 10,19 to 10,18 m2/s and agree with values found in the literature for similar systems. The rate constant for the intermediate conversion step is of the order of 10,6 s,1. This being among the first such determinations, this value awaits confirmation from other studies. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Fabrication and Characterization of Cordierite/Zircon Composites by Reaction Sintering: Formation Mechanism of ZirconJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 6 2002En-Hai Sun The formation mechanism of ZrSiO4 in the cordierite-ZrO2 system was studied in the temperature range of 1250° to 1400°C by X-ray diffraction analysis and discussed by analyzing experimental data using some reported reaction models. Nuclei growth models were found to describe the reaction well, and a satisfactory fit was obtained by applying the Avrami equation to estimate the reaction rate constant ,. Different values of the time exponent m were obtained at different temperatures: 0.32 at 1250°C, 0.34 at 1300°C, 0.39 at 1350°C, and 0.49 at 1400°C. The results indicate that there is a progressive change in reaction mechanism. [source] Determination of Optimum Conditions and the Kinetics of Methanol OxidationCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 1 2010A. H. Ulukardesler Abstract In this study, the catalytic oxidation of methanol to formaldehyde was investigated in a laboratory-scale fixed-bed catalytic reactor, under a large number of different conditions. Iron-molybdate catalysts supported by silica or alumina with a molybdenium/iron (Mo/Fe) ratio of 1.5, 3 and 5 were studied for the gas phase reaction. In order to obtain the optimum conditions, six different temperatures in the range of 250,375,°C and three different space times of 50.63, 33.75 and 20.25 g/(mol/h) were investigated. After determining the optimum conditions for this reaction, experiments aimed at understanding the reaction kinetics, were carried out. These experiments were performed on the catalyst favoring the formation of formaldehyde, which has a (Mo/Fe) ratio of 5 on a silica support. Seven reaction models derived by the mechanisms cited in the literature were tested to elucidate the kinetics of the reaction and the surface reaction controlling model was found to be the most suitable reaction mechanism. [source] The Roles of Gender and Affirmative Action Attitude in Reactions to Test Score Use Methods,JOURNAL OF APPLIED SOCIAL PSYCHOLOGY, Issue 9 2000Donald M. Truxillo The present study explored the effects of 2 variables, affirmative action (AA) attitude and gender, on reactions to 3 test score use (TSU) methods: top-down selection. banding with random selection, and banding with preferences. In a study of 94 upper-division and graduate business students, AA attitude was associated with different reactions to TSU methods in terms of fairness and organizational attractiveness. Moreover, women with negative AA attitudes and men rated banding with preferences lower than the other two methods, but women with positive AA attitudes did not Results are discussed in terms of applicant reactions models, implications for organizations and future research. [source] | ||||||||||