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Controlling Step (controlling + step)
Selected AbstractsKinetic study of the nitrosation of 1,3-dialkylureas in aqueous-perchloric acid mediumINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2004Guillermo González-Alatorre The kinetics of the nitrosation of 1,3-dimethyl (DMU), 1,3-diethyl (DEU), 1,3-dipropylurea (DPU), 1,3-dibuthyl (DBU), and 1,3-diallylurea (DAU) were studied in a conventional UV/vis spectrophotometer in aqueous-perchloric acid media. The kinetic study was carried out using the initial rate method. The reaction rate observed was where Ka is the acidity constant of nitrous acid. The diureas exhibited the reactivity order DMU , DEU > DPU > DAU, which can be interpreted as a function of the steric impediment generated by the R alkyl group in the rate controlling step. A probable relationship between both the chemical reactivity and structure of the nitrosable substrate with the biological activity of the N-nitroso compounds generated is proposed. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 273,279, 2004 [source] Palladium and platinum sorption on a thiocarbamoyl-derivative of chitosanJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010A. Butewicz Abstract Immobilizing thiourea onto chitosan allowed using the polymer for the recovery of platinum groups metals (PGMs) in acidic solutions (up to 1,2M HCl concentrations). At low HCl concentration protonated amine groups may sorb chloroanionic metal species (electrostatic attraction mechanism); however, most of sorption proceeds through chelation on sulfur containing groups (less sensitive to acidic conditions). The bi-site Langmuir equation was used for fitting sorption isotherms. The sorption of PGMs was weakly affected by the composition of the solution (presence of high concentration of anions and base metals). Maximum sorption capacities for Pd(II) and Pt(IV) ranged between 274 and 330 mg g,1 in 0.25M HCl solutions and decreased to 150,198 mg g,1 in 2M HCl solutions: Pd(II) sorption was systematically higher than Pt(IV) sorption. The pseudo-second rate equation was used for modeling the uptake kinetics. Agitation speed hardly affected uptake kinetics indicating that external diffusion resistance is not the rate controlling step. Desorption yield higher than 85% were obtained using thiourea in 0.1M HCl solution. The adsorbents could be reused for at least three cycles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Kinetics and mechanistic analysis of caustic magnesia hydrationJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 8 2004Sônia DF Rocha Abstract The kinetics of magnesia hydration to produce magnesium hydroxide is crucial for process design and control, and for the production of an Mg(OH)2 powder with desirable particle morphology. In this study, highly pure magnesia has been hydrated in a batch reactor. The effects of the following variables were evaluated experimentally: temperature (308,363 K), reaction time (0.5,5 h), initial slurry density (1,25%wt) and particle size in the ranges ,212 + 75 µm and ,45 + 38 µm. Experimental data indicate increasing magnesia hydration rates with increasing temperature, as expected. In addition, it has been observed that the hydration of magnesia increases significantly up to about 4,5%wt initial slurry density, stabilising afterwards. On the other hand, the reaction was almost unaffected when magnesia with different particle sizes were hydrated because of similar specific surface areas involved. A reaction mechanism to explain the oxide dissolution and the hydroxide precipitation has been proposed, assuming no significant change in the initial solids size and dissolution rate as the controlling step. The calculated activation energy value of 62.3 kJ mol,1 corroborates the mechanism proposed in this study and compares well with values previously reported in the literature. Copyright © 2004 Society of Chemical Industry [source] Explaining the enhanced performance of pulsed bioreactors by mechanistic modelingAICHE JOURNAL, Issue 5 2008Amaya Franco Abstract In this work, steady-state mass balance based models were applied to two UASB reactors and three UAF for a better understanding of the role of pulsation on the efficacy improvement. Models were defined taking into account the hydraulic behavior of each digester and the limiting mechanism of the overall process kinetics (mass transfer or biochemical reaction rate). The application of the model allows to identify that mass transfer was the controlling step in all the reactors, except for the nonpulsed UASB, where methanogenic activity controlled the reactor performance in the last operation steady states. Mass transfer coefficients were higher for pulsed reactors and, in general, a good agreement between those estimated by an empirical correlation and from the model was obtained. Damköhler number values supported that the external mass transfer resistance was not negligible with respect to the process kinetic and in addition, in most cases, it controls the overall process in the reactors. The relative importance of external and internal mass transfer rate was calculated through the Biot number. The values of this dimensionless module indicated that external transport was the main contributor to overall mass transfer resistance. © 2008 American Institute of Chemical Engineers AIChE J, 2008 [source] Chemically Bonded Phosphate Ceramics: I, A Dissolution Model of FormationJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 11 2003Arun S. Wagh This is the first of three papers in which the kinetics of formation of chemically bonded phosphate ceramics is discussed. A literature survey indicates that the formation of such ceramics is a three-step process. First, oxides dissolve in a phosphoric acid or an acid phosphate solution and metal ions are released into the solution. The aquoions formed from these cations then react with phosphate anions and form a gel of metal hydrophosphates. In the last step, the saturated gel crystallizes into a ceramic. In this paper, we have proposed that the dissolution is the controlling step and developed a general dissolution model of the kinetics of formation of these ceramics. As an example, the model is used to discuss the kinetics of formation of magnesium phosphate ceramics in detail. In the second and third papers, the model has been used to develop processes to form ceramics of alumina and iron oxides. [source] Temperature Dependence of Sol-Gel Conversion Kinetics in Gelatin-Water SystemMACROMOLECULAR BIOSCIENCE, Issue 4 2009Kai Chen Abstract The conversion kinetics of an aqueous gelatin solution to gel was studied by temperature modulated and regular DSC under isothermal and continuous cooling conditions. Isothermal runs revealed a decrease in the quasi-static heat capacity primarily associated with syneresis (phase separation) of the gel. Above 19,°C the isothermal process demonstrated negative effective activation energy that turned positive below 14,°C. Continuous cooling runs detected a reversing heat flow apparently related to the continuing formation and melting of new gel structures. Isoconversional kinetic analysis of continuous cooling measurements yielded negative activation energy for the whole range of conversions and temperatures suggesting that nucleation remained a rate controlling step throughout the whole gelation process. [source] Kinetic study of Fe removal from precipitated silica prepared from yellow phosphorus slagTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 4 2009Yi Su Abstract This purification process may be described by the unreacted shrink core model with solid resultant (inert material) and fixed particle size, which is carried out by the action of nitric acid solution on the precipitated silica obtained from yellow phosphorus slag which was leached with phosphoric acid. The study results indicate that the purification process is a chemical reaction controlling step and its apparent activation energy Ea is 30.354,kJ/mol, with reaction order 0.6746. Le présent procédé de purification peut être décrit par le modèle du noyau rétrécissant non réagi avec la résultante solide (matériau inerte) et la taille de particule fixe. Ce procédé est obtenu par l'action d'une solution d'acide nitrique sur une silice précipitée obtenue à partir des scories de phosphore lavées à l'acide phosphorique. Les résultats de l'étude montrent que le procédé de purification est une étape de contrôle de la réaction chimique, dont l'énergie d'activation apparente Ea est de 30,2354,kJ/mol, avec un ordre de réaction de 0,6746. [source] | |||||||||||||