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Reaction Order (reaction + order)
Selected AbstractsEstimation of Kinetic Parameters for Nonisothermal Food ProcessesJOURNAL OF FOOD SCIENCE, Issue 3 2003K.D. Dolan ABSTRACT This work deals with the hypothesis that kinetic parameters for nonisothermal processes can be reliably obtained using a 1-step method. Parameters were estimated for 3 typical processes: (1) no residence time distribution (RTD), (2) first-order reaction with RTD, and (3) nth-order reaction with RTD. When nonisothermal processes were approximated isothermally, k and ,E were underestimated 80% to 3 orders of magnitude, and 30% to 1 order of magnitude, respectively. Reaction order was overestimated by up to 0.81. Therefore, accounting for thermal history and RTD is critical to obtain accurate estimates of kinetic parameters. The 1-step method was also used to solve for equivalent isothermal temperatures and times for an arbitrary nonisothermal process. [source] Complete Elucidation of Electrode Reaction Mechanisms by Using Differential Pulse PolarographyELECTROANALYSIS, Issue 17-18 2010Miguel, Rodríguez Mellado Abstract By exploring the different parameters of the technique, it is shown that Differential Pulse Polarography (DPP) can be used for the elucidation of the reaction mechanisms of the electrochemical processes (with the evident exception of the product and intermediate identification). So, the type of transport towards or from the electrode can be identified from the dependence of the intensities with the pulse amplitude, the electrochemical reaction order with respect to the electroactive species from the shape of the polarogram, the type of rate-determining step from the dependence of the peak potentials on the pulse duration, the electrochemical reaction order with respect to other species, such as the H+ion, from the dependence of the peak potentials on their concentrations etc. [source] Effects of NO2, CO, O2, and SO2 on oxidation kinetics of NO over Pt-WO3/TiO2 catalyst for fast selective catalytic reduction processINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 10 2006Muhammad Faisal Irfan The selective catalytic reduction rate of NO with N-containing reducing agents can be enhanced considerably by converting a part of NO into NO2. The enhanced reaction rate is more pronounced at lower temperatures by using an equimolar mixture of NO and NO2. The kinetics of NO oxidation over Pt-WO3/TiO2 catalyst has been determined in a fixed-bed reactor with different concentrations of oxygen, nitric oxide, and nitrogen dioxide in the presence of 8% water. It has been found that the reaction is second order with respect to nitric oxide, first order for oxygen with a third-order rate constant. Also, it is found that there is no effect on the reaction order with an addition of NO2, CO, or SO2. It follows the same second order but the reaction rate is found to be changed. It is observed that in the case of NO2 and SO2, the reaction rate tends to decrease, but it increases with the addition of CO into the feed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 613,620, 2006 [source] The nonisothermal decomposition kinetics of copper(II) complexes with phthalanilic acids and amino acidsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2003Li-Ping Ren Fifteen new kinds of mixed ligand complexes Cu(x-P)A [P = 2-(COO)C6H4CONH-C6H4; x = H, 2-Cl, 2-CH3, 2-OCH3, 4-OCH2CH3; A = dehydronium Met, Leu, Phen] were synthesized. The thermal decomposition behavior of each complex is studied by TG. Coats--Redfern, MacCallum--Tammer, and Zsako methods are adopted to estimate the values of the apparent activation energy Ea, the activation entropy ,S,, the reaction order n, and the frequency factor A. The results showed that the reaction order is 2/3 for each of the complex. Studies on the mechanism of the thermal decomposition reactions suggested that these reactions all fit the kinetic equation 1 , (1 , ,)1/3 = © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 623,628, 2003 [source] Formation and decay of the ABTS derived radical cation: A comparison of different preparation proceduresINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2002Carola Henriquez Bleaching of a preformed solution of the blue-green radical cation 2,2,-azinobis (3-ethylbenzothizoline-6-sulfonic acid) (ABTS+·) has been extensively used to evaluate the antioxidant capacity of complex mixtures and individual compounds. The reaction of the preformed radical with free-radical scavengers can be easily monitored by following the decay of the sample absorbance at 734 nm. The ABTS radical cation can be prepared employing different oxidants. Results obtained using MnO2 as oxidant show that the presence of manganese ions increases the rate of [ABTS]+· autobleaching in a concentration-dependent manner. The radicals can also be obtained by oxidizing ABTS with 2,2, -azobis(2-amidinopropane)hydrochloride (AAPH) or peroxodisulfate (PDS). The oxidation by AAPH takes place with a large activation energy and a low reaction order in ABTS. The data support a mechanism in which the homolysis of AAPH is the rate-limiting step, followed by the reaction of ABTS with the peroxyl radicals produced after the azocompound thermolysis. On the other hand, the low activation energy measured employing PDS, as well as the kinetic law, are compatible with the occurrence of a bimolecular reaction between the oxidant and ABTS. Regarding the use of ABTS-based methodologies for the evaluation of free radical scavengers, radical cations obtained employing AAPH as oxidant can be used only at low temperatures, conditions where further decomposition of the remaining AAPH is minimized. The best results are obtained with ABTS derived radicals generated in the reaction of PDS with an ABTS/PDS concentration ratio equal (or higher) to two. However, even with radicals prepared by this procedure, stoichiometric coefficients considerably larger than two are obtained for the consumption of the radical cation employing tryptophane or p -terbutylphenol as reductants. This casts doubts on the use of ABTS-based procedures for the estimation of antioxidant capacities. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 659,665, 2002 [source] New method for kinetic analysis of decomposition of biomass materials,Based on critical analysis of Moll methodJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2009Naian Liu Abstract Moll method used in extracting the kinetic parameters of thermal decomposition of biomass materials is theoretically analyzed and the limitation of the method is critically examined. It is demonstrated that Moll method can only be used under strict conditions within narrow temperature intervals. In light of the idea of Moll method and also in view of the limitations of Moll method, a two-point data set method is developed for the kinetic analysis of the decomposition of biomass materials in air, using single heating rate mass-loss curve. The method is justified by comparing the resulted kinetic parameters with those by integral and differential methods. Compared with Moll method, the new method is applicable to the mass-loss data within wide temperature intervals, whereby the kinetic parameters (especially the activation energy) can be evaluated without any prior knowledge of reaction order, with fairly high reliability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Synthesis, characterization, and kinetic of thermal degradation of oligo-2-[(4-bromophenylimino)methyl]phenol and oligomer-metal complexesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009smet Kaya Abstract Oligo-2-[(4-bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2-[(4-bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet,visible spectrophotometer (UV,vis), 1H-NMR, and 13C-NMR analyses. The characterization was made by TG-DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer-metal complexes with Co+2, Ni+2, and Cu+2 ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats-Redfern, MacCallum-Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (Ea), the reaction order (n), preexponential factor (A), the entropy change (,S*), enthalpy change (,H*), and free energy change (,G*) obtained by earlier-mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Supercritical water oxidation of quinoline in a continuous plug flow reactor,part 2: kineticsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2006Lisete DS Pinto Abstract The results of a detailed investigation into the kinetics of quinoline oxidation in supercritical water are presented. The novel kinetic data presented were obtained in a continuously operated, plug flow reactor where parameters such as temperature, pressure, residence time and stoichiometric ratio of oxidant to quinoline were investigated and detailed in the companion paper (Pinto LDS, Freitas dos Santos LMF, Al-Duri B and Santos RCD, Supercritical water oxidation of quinoline in a continuous plug flow reactor,part 1: effect of key operating parameters. J Chem Technol Biotechnol). An induction time was experimentally observed, ranging from 1.5 to 3.5 s, with longer times observed in experiments carried out at lower temperatures. A pseudo-first-order rate expression with respect to quinoline concentration (with oxygen excess) was first adopted and the activation energy of 234 kJ mol,1 and a pre-exponential factor of 2.1 × 1014 s,1 were estimated. Furthermore, an integral power rate model expression was established, attributing a reaction order for quinoline as 1 and for oxygen as 0.36. An activation energy and pre-exponential factor for this model were determined as 224 kJ mol,1 and 3.68 × 1014 M,0.36 s,1, respectively. A global rate expression was then regressed for the quinoline reaction rate from the complete set of data. The resulting activation energy was 226 ± 19 kJ mol,1 and the pre-exponential factor was 2.7 × 1013 ± 2 M,0.1 s,1. The reaction orders for quinoline and oxygen were 0.8 ± 0.1 and 0.3 ± 0.1, respectively. It was shown that the least-squares regression method provided the best-fit model for experimental results investigated in this study. Copyright © 2006 Society of Chemical Industry [source] Kinetics of Formation and Physicochemical Characterization of Thermally-Induced ,-Lactoglobulin AggregatesJOURNAL OF FOOD SCIENCE, Issue 5 2010R.N. Zúñiga Abstract:, The kinetics of heat denaturation and aggregation for ,-lactoglobulin dispersions (5% w/v) were studied at 3 pHs (6, 6.4, and 6.8) and at a heating temperature of 80 °C. Protein aggregates were characterized for hydrodynamic diameter, microstructure, and molecular weight by means of dynamic light scattering, transmission electron microscopy, and polyacrylamide gel electrophoresis, respectively. Concentration of native ,-lactoglobulin decreased with holding time and with a decrease in the pH. Apparent rate constants were calculated for ,-lactoglobulin denaturation applying the general kinetic equation solved for a reaction order of 1.5. Values of the apparent reaction rate constant,k,= 7.5, 6.3 and 5.6 × 10,3 s,1 were found for pH 6, 6.4, and 6.8, respectively. Decreasing the pH of the dispersions produced higher aggregate sizes. After a holding time of 900 s, average hydrodynamic diameters for ,-lactoglobulin aggregates at pH 6, 6.4, and 6.8 were 96, 49, and 42 nm, respectively. These results were confirmed by transmission electron microscopy images, where a shift in the size and morphology of aggregates was found, from large and spherical at pH 6 to smaller and linear aggregates at pH 6.8. ,-Lactoglobulin formed disulfide-linked intermediates (dimers, trimers, tetramers) and so on) which then formed high molecular weight aggregates. From the results obtained by DLS, TEM, and SDS-PAGE a mechanism for ,-lactoglobulin aggregation was proposed. This study shows that heat treatment can be used to produce protein aggregates with different sizes and morphologies to be utilized as ingredients in foods. [source] A Kinetic Study on the Thermal Degradation of Multi-Walled Carbon Nanotubes-Reinforced Poly(propylene) CompositesMACROMOLECULAR MATERIALS & ENGINEERING, Issue 4 2004Min-Kang Seo Abstract Summary: The influence of the multi-walled carbon nanotubes (MWNTs) content on the thermal degradation behavior of MWNTs-reinforced poly(propylene) (PP) composites was investigated by using non-isothermal thermogravimetric analysis (TGA). Kinetic parameters of degradation were evaluated by using the Flynn-Wall-Ozawa iso-conversional method and the pseudo first-order method. As a result, compared with pristine PP, MWNTs-PP nanocomposites have lower peak temperatures of degradation, narrower degradation temperature ranges and a higher amount of residual weight at the end of the degradation, which is likely to be a result of specific interactions between complimentary functional groups. The values of the reaction order of MWNTs-PP nanocomposites determined by the Kissinger method are close to 1 in the non-isothermal degradation process. There is a good correlation between the Ea in region II and the peak temperature of degradation for the composites. Activation energies for degradation of different contents of MWNTs-filled PP nanocomposites as a function of conversion. [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] Catalysts for water,gas shift processing of coal-derived syngases,ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 4 2010San Shwe Hla Abstract Although the gasification of coal is an efficient means of producing syngas, the carbon content of coal is such that gasification produces significantly higher ratios of carbon oxides to hydrogen than those obtained by the steam reforming of natural gas. The CO:H2 ratio can be adjusted, and more hydrogen produced, by the subsequent application of the water,gas shift (WGS) reaction. This article presents a review of technologies associated with the catalytic WGS reaction in a fixed-bed reactor that might be incorporated into a coal gasification-based system for H2 production with CO2 capture. The main output from this review is the identification of key project areas requiring further research. The performance of existing, commercially available catalysts,designed for use in natural gas reforming processes,with coal-derived syngases is an important aspect of developing technologies for coal-based H2 production. This article presents an experimental assessment of the performance of selected commercially available WGS catalysts, two high-temperature catalysts (HT01 and HT02) and a sour shift catalyst (SS01), with such syngases. For the three commercial catalysts investigated in this study, CO reaction order is found to be in a range of 0.75,1. The effect of changes in H2O concentration over HT01 is insignificant, whereas H2O reaction orders determined using HT02 and SS01 are found to be significantly positive even at high H2O:C ratios. The CO conversion rate is significantly reduced by increasing CO2 concentration, whereas increasing H2 concentration also causes a slight reduction in CO conversion rate for the three commercial catalysts investigated. Copyright © 2010 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Kinetic Study of the Asymmetric Hydrogenation of Methyl Acetoacetate in the Presence of a Ruthenium Binaphthophosphepine ComplexADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Eva Öchsner Abstract The asymmetric hydrogenation of methyl acetoacetate (MAA) in methanol using dibromobis{(S)-4-phenyl-4,5-dihydro-3H -dinaphtho[2,1- c: 1,,2,- e]phosphepine}-ruthenium was studied in detail. For the determination of the reaction network, data from kinetic experiments were compared to different possible reaction networks using the kinetic software Presto Kinetics. The simulation was optimised to describe the reaction accurately with a minimal set of process parameters and reaction equations. For the best model the reaction orders, collision factors and activation energy of all reaction steps were determined. Additionally, the influence of reaction temperature and hydrogen pressure on the enantiomeric excess (ee) of the reaction was studied. It was found that high reaction temperatures and high hydrogen pressures result in increasing enantioselectivities. [source] Kinetics and thermodynamics of isothermal curing reaction of epoxy-4, 4,-diaminoazobenzene reinforced with nanosilica and nanoclay particlesPOLYMER COMPOSITES, Issue 8 2010M. Barghamadi The kinetics of the cure reaction for a system of bisphenol-A epoxy resin (DGEBA), with 4, 4,-diaminoazobenzene (DAAB), reinforced with nanosilica (NS), and nanoclay (NC) by means of isothermal technique of differential scanning calorimetry were studied. The Kamal autocatalytic-like kinetic model was used to estimate the reaction orders (m, n), rate constants (k1, k2), and also active energies (Ea) and pre-exponential factors (A) of the curing reaction. However, the existence of NS and NC with hydroxyl groups in the structure improves the cure reaction and influence the rate of reaction and therefore kinetics parameters. The Ea of cure reaction of DGEBA/DAAB system showed a decrease when nanoparticles were present and therefore the rate of the reaction was increased. Using the rate constants from the kinetic analysis and transition state theory, thermodynamic parameters such as enthalpy (,H#), entropy (,S#), and Gibbs free energy (,G#) changes were also calculated. The thermodynamic functions were shown to be very sensitive parameters for evaluation of the cure reaction. POLYM. COMPOS., 31:1442,1448, 2010. © 2009 Society of Plastics Engineers [source] Mechanism study on carbon reducing reaction in the preparation process of strontium carbonate (SrCO3)ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2009Jun Meng Abstract The mechanism for preparation of strontium carbonate (SrCO3) by the method of carbon reducing reaction is studied in this paper. Based on the mass ratio of SrSO4/C = 1.5 for this reaction, thermodynamics and kinetics calculation are conducted and also verified by TG-DSC experimental methods. For each side reaction, the changes of standard molar Gibbs function at proposed temperature are calculated through Gibbs-Helmholtz, Van't Hoff and Kirchhoff equations. TG-DSC data are used to explore the mechanism of the reaction, and to calculate the apparent activation energy and reaction orders. It has been demonstrated by TG and DSC thermal analysis for the whole reducing reaction that the apparent activation energy E is 350.6 and 307.3 kJ·mol,1, and the reaction orders n are 0.91 and 0.88, respectively. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Absorption Rate of Carbon Dioxide by K2CO3 -KHCO3 DEA Aqueous SolutionASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 1-2 2005K. Takahshi Gas absorption rates of carbon dioxide from CO2 -air mixtures into K2CO3, K2CO3 -KHCO3, DEA and K2CO3 -KHCO3 -DEA solutions have been measured by using a wetted wall column. The method to determine the enhancement factor of chemical absorption is confirmed by the absorption of carbon dioxide in NaOH solution. The enhancement factor was correlated with the potassium concentration [K+] (= 2[K2CO3 + [KHCO3]), the DEA concentration, and the CO2 -loading ratio of the absorbent. The chemical reaction for CO2, absorption has been expressed by an (m,n)th order irreversible-reaction model, where the reaction orders are m = 1 for CO2, n = 1.35 for DEA, n = 0.6 for K2CO3, and n = 0.6 and 1.35 for K2CO3 and DEA respectively. Experimental values of the enhancement factor were successfully reproduced by the calculations, where the reaction rate constants reflected the effect of loading ratio of the absorbent with carbon dioxide. [source] Decomposition of Formic Acid Catalyzed by a Phosphine-Free Ruthenium Complex in a Task-Specific Ionic LiquidCHEMCATCHEM, Issue 10 2010Jackson D. Scholten Abstract The dehydrogenation of formic acid is effectively catalyzed by the Ru complex [{RuCl2(p -cymene)}2] dissolved in the ionic liquid (IL) 1-(2-(diethylamino)ethyl)-3-methylimidazolium chloride at 80,°C without additional bases. This catalytic system gives TOF values of up to 1540,h,1. Preliminary kinetic insights show formal reaction orders of 0.70(±0.15), 0.78(±0.03) and 2.00(±0.17) for the Ru catalyst, IL,1, and formic acid, respectively. The apparent activation energy of this process is estimated to be (69.1±7.6),kJ,mol,1. In addition, dimeric Ru hydride ionic species involved in the reaction, such as [{Ru(p -cymene)}2{(H),-(H)-,-(HCO2)}]+ and [{Ru(p -cymene)}2{(H),-(Cl),-(HCO2)}]+, are identified by mass spectrometry. The presence of water in large amounts inhibits higher conversions. Finally, a remarkable catalytic activity is observed during recycles, indicating this system's potential for hydrogen gas production. [source] Kinetic 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] | |||||||||||||