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Reaction Kinetics (reaction + kinetics)
Kinds of Reaction Kinetics Selected AbstractsInfluence of Point-Defect Reaction Kinetics on the Lattice Parameter of Ce0.8Gd0.2O1.9ADVANCED FUNCTIONAL MATERIALS, Issue 4 2009Anna Kossoy Abstract The kinetics of point-defect association/dissociation reactions in Ce0.8Gd0.2O1.9 and their influence on the crystal lattice parameter are investigated by monitoring thermally induced stress and strain in substrate- and self-supported thin films. It is found that, in the temperature range of 100,180,°C, the lattice parameter of the substrate-supported films and the lateral dimensions of annealed, self-supported films both exhibit a hysteretic behavior consistent with dissociation/association of oxygen vacancy,aliovalent dopant complexes. This leads to strong deviation from linear elastic behavior, denoted in the authors' previous work as the "chemical strain" effect. At room temperature, the equilibrium state of the point defects is reached within a few months. During this period, the lattice parameter of the substrate-supported films spontaneously increases, while the self-supported films are observed to transform from the flat to the buckled state, indicating that formation of the dopant,vacancy complex is associated with a volume increase. The unexpectedly slow kinetics of establishing the defect equilibrium at room temperature can explain the fact that, depending on the sample history, the "observable" lattice parameters of Ce0.8Gd0.2O1.9, as reported in the literature, may differ from one another by a few tenths of a percent. These findings strongly suggest that the lattice parameter of the materials with a large concentration of interacting point defects is a strong function of time and material preparation route. [source] Improving the Hydrogen Reaction Kinetics of Complex HydridesADVANCED MATERIALS, Issue 29 2009Jun Yang Abstract Alanates, borohydrides, and amides are complex hydrides with high concentration hydrogen that have been actively investigated for materials-based hydrogen storage on-board polymer electrolyte membrane fuel cell (PEMFC) vehicle applications. The major challenge is to release hydrogen at fuel cell working temperature range at fast enough rate without simultaneous desorption of fuel cell poisoning impurities. We review recent progress in hydrogen reaction mechanism and schemes for complex hydride hydrogen storage. [source] Effects of pH on Caramelization and Maillard Reaction Kinetics in Fructose-Lysine Model SystemsJOURNAL OF FOOD SCIENCE, Issue 7 2001E.H. Ajandouz ABSTRACT: The nonenzymatic browning reactions of fructose and fructose-lysine aqueous model systems were investigated at 100 °C between pH 4.0 and pH 12.0 by measuring the loss of reactants and monitoring the pattern of UV-absorbance and brown color development. At all the pH values tested, the loss of fructose was lower in the presence than in the absence of lysine. And, in lysine-containing fructose solution, the sugar disappeared more rapidly than the amino acid. Lysine was moderately lost below pH 8.0. Caramelization of fructose, which accounted for more than 40% of total UV-absorbance and 10 to 36% of brown color development, may therefore lead to overestimating the Maillard reaction in foods. [source] Influence of Activation Temperature on Reaction Kinetics in Recycled Clay Waste,Calcium Hydroxide SystemsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2008Moisés Frías Obtaining pozzolanic materials from recycling of industrial waste and byproducts is a priority action of environmental policy all over the world. This paper describes the effect of activation conditions on the reaction kinetics in calcined clay waste (CCW)/calcium hydroxide systems. The CCW used in this work shows excellent qualities for use as supplementary cementing material in the manufacture of commercial blended cements. This research work presents an exhaustive study about the kinetics of a pozzolanic reaction in this cementing system. The results obtained by different techniques (DTA/TG, X-ray diffraction, and SEM/EDAX) confirm that the activation conditions (in the range 700°,800°C and 2,5 h of retention) have a direct effect on the formation and evolution of hydrated phases. Low activation temperatures favor the CSH gels' formation, while at higher temperatures aluminates (C4AH13) and aluminum silicate hydrates (C4ASH8, hydrotalcites) are predominant. [source] Solid-State Synthesis of Nanocrystalline BaTiO3: Reaction Kinetics and Powder PropertiesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 9 2008Maria Teresa Buscaglia The formation of BaTiO3 nanoparticles by a solid-state reaction between nanocrystalline raw materials BaCO3 and TiO2 was studied as a function of temperature (400°,800°C), time (1,24 h), and titania particle size (15 and 30 nm). The reaction starts at 500°C and a high reaction rate is already observed at 600°C for the finest titania, with up to 90% conversion after 2 h. Two main reaction stages were observed at 600°,700°C. The first step is dominated by nucleation and growth of BaTiO3 at the TiO2,BaCO3 contact points and at the TiO2 surface. Surface diffusion of BaCO3 is, most likely, the prevailing mass transport mechanism responsible for the rapid formation of BaTiO3, even in the absence of a significant contribution from lattice diffusion. The second stage begins when the residual TiO2 cores are completely covered by the product phase. For longer times, the reaction can only proceed by the slower lattice diffusion, resulting in a strong decrease of the reaction rate. Single-phase BaTiO3 nanopowders with a specific surface area of 12,15 m2/g, an average particle size of 70,85 nm, a relative density of 96.5%,98.3%, and a tetragonality of 1.005 were obtained by calcination at 700°,800°C. Critical parameters in the preparation of ultrafine powders by solid-state reactions are the particle size of both raw materials, the absence of large hard agglomerates, and the homogeneity of the mixture. The use of fine raw materials and optimization of the reaction conditions make mechanical activation unnecessary. [source] Runaway Reaction Kinetics for Emulsion Polymerization and its ConsequencesMACROMOLECULAR REACTION ENGINEERING, Issue 5-6 2009Lambertus G. Manders Abstract For industrial semi-batch emulsion polymerization, it is difficult to predict the composition of the reactor contents during a runaway reaction since many recipes are involved and it actually may be a fault in the feeds to the reactor that leads to the runaway reaction, as a distributed control system cannot safely prevent wrong feeds. Therefore, in order to safeguard the reactor, very high kinetics need to be taken into account, as discussed theoretically as well as based on an example. Corresponding maximum temperature increase rates may be above 100 K,·,min,1. This needs to be taken into account when designing safety measures for emulsion polymerization reactions. As a result, large safety relief valves or rupture discs may need to be installed. [source] Reaction Kinetics of Soybean Oil Transesterification Using Heterogeneous Metal Oxide CatalystsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 12 2007K. Singh Abstract Homogeneous acid or base catalysts dissolve fully in the glycerol layer and partially in the fatty acid methyl ester (biodiesel) layer in the triglyceride transesterification process. Heterogeneous (solid) catalysts, on the other hand, can prevent catalyst contamination making product separation much simpler. In the present work, the transesterification kinetics of five different solid catalysts with soybean oil is presented. It is found that heterogeneous catalysts require much higher temperatures and pressures to achieve acceptable conversion levels compared to homogeneous catalysts. Subsequent to preliminary investigations, transesterifications were conducted for selected high performance solid catalysts, i.e., MgO, CaO, BaO, PbO, and MnO2 in a high pressure reactor up to a temperature of 215,°C. The yield of the fatty acid methyl esters and the kinetics (rate constant and order) of the reaction are estimated and are compared for each catalyst. [source] Real-Time Monitoring of Mass-Transport-Related Enzymatic Reaction Kinetics in a Nanochannel-Array ReactorCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2010Su-Juan Li Abstract To understand the fundamentals of enzymatic reactions confined in micro-/nanosystems, the construction of a small enzyme reactor coupled with an integrated real-time detection system for monitoring the kinetic information is a significant challenge. Nano-enzyme array reactors were fabricated by covalently linking enzymes to the inner channels of a porous anodic alumina (PAA) membrane. The mechanical stability of this nanodevice enables us to integrate an electrochemical detector for the real-time monitoring of the formation of the enzyme reaction product by sputtering a thin Pt film on one side of the PAA membrane. Because the enzymatic reaction is confined in a limited nanospace, the mass transport of the substrate would influence the reaction kinetics considerably. Therefore, the oxidation of glucose by dissolved oxygen catalyzed by immobilized glucose oxidase was used as a model to investigate the mass-transport-related enzymatic reaction kinetics in confined nanospaces. The activity and stability of the enzyme immobilized in the nanochannels was enhanced. In this nano-enzyme reactor, the enzymatic reaction was controlled by mass transport if the flux was low. With an increase in the flux (e.g., >50,,L,min,1), the enzymatic reaction kinetics became the rate-determining step. This change resulted in the decrease in the conversion efficiency of the nano-enzyme reactor and the apparent Michaelis,Menten constant with an increase in substrate flux. This nanodevice integrated with an electrochemical detector could help to understand the fundamentals of enzymatic reactions confined in nanospaces and provide a platform for the design of highly efficient enzyme reactors. In addition, we believe that such nanodevices will find widespread applications in biosensing, drug screening, and biochemical synthesis. [source] Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to ,-Oxodiiron(III) Complexes and Effect of ,-Fluorination on the Reaction KineticsCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2008Nasser Abstract We have synthesized the mono, di-, and tri-,-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, F2TPA and F3TPA, respectively. Fluorination at the ,-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45,70,mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and F2TPA reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in TPAFeCl2. All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable ,-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three ,-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the ,4N coordination mode. With FTPA, the compound is a neutral ,-oxodiiron(III) complex with a ,3N coordination mode of the ligand. Oxygenation of the F2TPA complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all ,-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of ,-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90,% conversion over 40,h, the monofluorinated ligand provides a complex that has fully reacted after 30,h, whereas the reaction time for the complex with the difluorinated ligand is only 10,h. Analysis of the spectroscopic data reveals that formation of the ,-oxo complexes proceeds in two distinct reversible kinetic steps with k1,10,k2. For TPAFeCl2 and FTPAFeCl2 only small variations in the k1 and k2 values are observed. By contrast, F2TPAFeCl2 exhibits k1 and k2 values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of ,-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials. [source] Thermal Behavior and Non-isothermal Decomposition Reaction Kinetics of NEPE Propellant with Ammonium DinitramideCHINESE JOURNAL OF CHEMISTRY, Issue 5 2010Weiqiang Pang Abstract Thermal decomposition behavior and non-isothermal decomposition reaction kinetics of nitrate ester plasticized polyether NEPE propellant containing ammonium dinitramide (ADN), which is one of the most important high energetic materials, were investigated by DSC, TG and DTG at 0.1 MPa. The results show that there are four exothermic peaks on DTG curves and four mass loss stages on TG curves at a heating rate of 2.5 K·min,1 under 0.1 MPa, and nitric ester evaporates and decomposes in the first stage, ADN decomposes in the second stage, nitrocellulose and cyclotrimethylenetrinitramine (RDX) decompose in the third stage, and ammonium perchlorate decomposes in the fourth stage. It was also found that the thermal decomposition processes of the NEPE propellant with ADN mainly have two mass loss stages with an increase in the heating rate, that is the result of the decomposition heats of the first two processes overlap each other and the mass content of ammonium perchlorate is very little which is not displayed in the fourth stage at the heating rate of 5, 10, and 20 K·min,1 probably. It was to be found that the exothermal peak temperatures increased with an increase in the heating rate. The reaction mechanism was random nucleation and then growth, and the process can be classified as chemical reaction. The kinetic equations of the main exothermal decomposition reaction can be expressed as: d,/dt=1012.77(3/2)(1,,)[,ln(1,,)]1/3 e,1.723×104/T. The critical temperatures of the thermal explosion (Tbe and Tbp) obtained from the onset temperature (Te) and the peak temperature (Tp) on the condition of ,,0 are 461.41 and 458.02 K, respectively. Activation entropy (,S,), activation enthalpy (,H,), and Gibbs free energy (,G,) of the decomposition reaction are ,7.02 J·mol,1·K,1, 126.19 kJ·mol,1, and 129.31 kJ·mol,1, respectively. [source] Non-isothermal Decomposition Reaction Kinetics of the Magnesium Oxalate DihydrateCHINESE JOURNAL OF CHEMISTRY, Issue 3 2006Jian-Jun Zhang Abstract The thermal decomposition of the magnesium oxalate dihydrate in a static air atmosphere was investigated by TG-DTG techniques. The intermediate and residue of each decomposition were identified from their TG curve. The kinetic triplet, the activation energy E, the pre-exponential factor A and the mechanism functions f(,) were obtained from analysis of the TG-DTG curves of thermal decomposition of the first stage and the second stage by the Popescu method and the Flynn-Wall-Ozawa method. [source] Reaction kinetics for the degradation of phenol and chlorinated phenols using Fenton's reagentENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 1 2006Asim K. De Abstract Fenton's reaction is an advanced treatment technology often used for the removal of hazardous and refractory organic compounds from industrial wastewaters. It can effectively be used to degrade phenol and chlorophenols. The initial contaminant concentrations as well as the concentration of hydrogen peroxide and ferrous ions in aqueous solution have a significant effect on the effective degradation of contaminants. For a particular concentration of initial substrate in solution there should be an optimum level of ferrous ion concentration in the reaction medium. Based on experimental observations, a probable mechanism for Fenton's degradation kinetics has been proposed and a rate equation developed. From the rate expression, OH· radical reaction rate constants for the degradation of three compounds,phenol and o- and p-chlorophenols,in Fenton reaction were calculated to have values of 2.53 × 107, 2.38 × 107, and 2.45 × 107 m3 mol,1 s,1, respectively. © 2005 American Institute of Chemical Engineers Environ Prog, 2005 [source] Pyrazole formation: Examination of kinetics, substituent effects, and mechanistic pathways,INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2008Joseph C. Sloop Reaction kinetics for the condensation of 1,3-diketones 1a,o with selected arylhydrazines (aryl = Ph, 4-NO2Ph, 4-CH3OPh, and 2,4-diNO2Ph) was studied using 19F NMR spectroscopy. Product regioselectivity is modulated by reactant ratios, substituents, and acidity. Reaction rates were found to be influenced by substituents on the diketones and on phenylhydrazines as well as by acidity of the reaction medium with rates varying as much as 1000-fold. Hammett , values for these cyclizations were determined. The reaction was found to be first order in both the diketone and arylhydrazine. The rate-determining step for pyrazole formation shifts as a function of pH. Mechanistic details and reaction pathways supporting these findings are proposed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 370,383, 2008 [source] Reaction kinetics of graft copolymerization and thermochemical studies of the degradation of poly(vinyl alcohol) graft copolymerPOLYMER INTERNATIONAL, Issue 3 2001Yassin A Aggour Abstract Poly(vinyl alcohol) (PVA) is a water-soluble and biomedical polymer. 2-Acrylamido-2-methyl-1-propanesulfonic acid was grafted onto PVA using ammonium persulfate as radical initiator. The influences of synthesis conditions such as temperature, concentrations of initiator, PVA and monomer were investigated. Both the initial rate of grafting and the final percentage of grafting were increased by an increase in reaction temperature. The reaction kinetics were studied to determine the rate constants of the first-order reactions. An activation energy of 16.3,kJ,mol,1 was found for the grafting reaction. The graft copolymers were characterized by IR and intrinsic viscosity measurements. A proposed mechanism of the grafting reaction is discussed. Kinetics of the thermal degradation were studied using a thermogravimetric method and the order of thermal stabilities are given. The apparent activation thermodynamic parameters, Ea, ,H*, ,S* and ,G* were determined and correlated to the thermal stabilities of the homo- and grafted polymers. © 2001 Society of Chemical Industry [source] Generalized treatment of NMR spectra for rapid chemical reactionsCONCEPTS IN MAGNETIC RESONANCE, Issue 4 2007Matthew D. Christianson Abstract Application of NMR spectroscopy to fast irreversible reactions (t1/2 < 0.7 s) has been hampered by limitations in instrumentation and general methods for modeling the complicated spectra that result. Analytical descriptions of nuclear spin dynamics during fast reactions, first solved by Ernst and coworkers, are limited to first-order reaction kinetics. We demonstrate that numeric methods enable simulation of NMR spectra for fast reactions having any form of rate law. Simulated stopped-flow NMR spectra are presented for a variety of common kinetic scenarios including reversible and irreversible reactions of first and second-order, multistep reactions, and catalytic transformations. The simulations demonstrate that a wealth of mechanistic information, including reaction rates, rate laws, and the existence of intermediates, is imbedded in a single NMR spectrum. The sensitivity of modern NMR instrumentation along with robust methods for simulating and fitting kinetic parameters of fast reactions make stopped-flow NMR an attractive method for kinetic studies of fast chemical reactions. © 2007 Wiley Periodicals, Inc. Concepts Magn Reson Part A 30A: 165,183, 2007. [source] A novel approach for analysis of oligonucleotide,cisplatin interactions by continuous elution gel electrophoresis coupled to isotope dilution inductively coupled plasma mass spectrometry and matrix-assisted laser desorption/ionization mass spectrometryELECTROPHORESIS, Issue 7 2008Wolfram Brüchert Abstract In this work we present a novel approach for in vitro studies of cisplatin interactions with 8-mer oligonucleotides. The approach is based on the recently developed coupling of continuous elution gel electrophoresis (GE) to an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS) with the aim of monitoring the interaction process between this cytostatic drug and the nucleotides. In contrast to existing methods, the electrophoretic separation conditions used here allow both the determination of the reaction kinetics in more detail as well as the observation of dominant intermediates. Two different nucleotides sequences have been investigated for comparison purposes, one containing two adjacent guanines (5,-TCCGGTCC-3,) and one with a combination of thymine and guanine (5,-TCCTGTCC-3,), respectively. In order to gain further structural information, MALDI-TOF MS measurements have been performed after fraction collection. This allows for identification of the intermediates and the final products and confirms the stepwise coordination of cisplatin via monoadduct to bisadduct formation. Furthermore, the ICP-MS results were quantitatively evaluated in order to calculate the kinetics of the entire process. [source] Dual injection capillary electrophoresis: Foundations and applicationsELECTROPHORESIS, Issue 23-24 2004Feliciano Priego-Capote Abstract The state of the art of capillary electrophoresis (CE) approaches based on dual injection is here reported. Dual injection strategies have been proposed with three main objectives: (i) to provide information about reaction kinetics and/or related parameters, (ii) to perform in-capillary derivatization for improving separation and/or determination, (iii) to develop electrophoretic methods for the simultaneous analysis of anionic and cationic compounds. For the first two purposes, dual injection, which involves sample and reagent, can be realized either from the same end of the capillary (electrophoretically mediated microanalysis, EMMA) or from the two ends of the capillary (electroinjection analysis, EIA). The third objective, with dual injection of sample from the two ends of the capillary, takes advantage of moving cationic and anionic compounds with opposite directions. The foundations of each alternative, conditions necessary for working with them, restrictions, applications as well as perspectives are reviewed in order to establish the advantages, shortcomings, and convenience or no of their use in comparison to conventional CE. [source] Integrated on-chip derivatization and electrophoresis for the rapid analysis of biogenic aminesELECTROPHORESIS, Issue 14 2004Nigel P. Beard Abstract We demonstrate the monolithic integration of a chemical reactor with a capillary electrophoresis device for the rapid and sensitive analysis of biogenic amines. Fluorescein isothiocyanate (FITC) is widely employed for the analysis of amino-group containing analytes. However, the slow reaction kinetics hinders the use of this dye for on-chip labeling applications. Other alternatives are available such as o -phthaldehyde (OPA), however, the inferior photophysical properties and the UV ,max present difficulties when using common excitation sources leading to a disparity in sensitivity. Consequently, we present for the first time the use of dichlorotriazine fluorescein (DTAF) as a superior in situ derivatizing agent for biogenic amines in microfluidic devices. The developed microdevice employs both hydrodynamic and electroosmotic flow, facilitating the creation of a polymeric microchip to perform both precolumn derivatization and electrophoretic analysis. The favorable photophysical properties of the DTAF and its fast reaction kinetics provide detection limits down to 1 nM and total analysis times (including on-chip mixing and reaction) of <60 s. The detection limits are two orders of magnitude lower than current limits obtained with both FITC and OPA. The optimized microdevice is also employed to probe biogenic amines in real samples. [source] Reversible and High-Capacity Nanostructured Electrode Materials for Li-Ion BatteriesADVANCED FUNCTIONAL MATERIALS, Issue 10 2009Min Gyu Kim Abstract Reversible nanostructured electrode materials are at the center of research relating to rechargeable lithium batteries, which require high power, high capacity, and high safety. The higher capacities and higher rate capabilities for the nanostructured electrode materials than for the bulk counterparts can be attributed to the higher surface area, which reduces the overpotential and allows faster reaction kinetics at the electrode surface. These electrochemical enhancements can lead to versatile potential applications of the batteries and can provide breakthroughs for the currently limited power suppliers of mobile electronics. This Feature Article describes recent research advances on nanostructured cathode and anode materials, such as metals, metal oxides, metal phosphides and LiCoO2, LiNi1,xMxO2 with zero-, one-, two-, and three-dimensional morphologies. [source] The Selective Heating of Iron Nanoparticles in a Single-Mode Microwave for the Patterned Growths of Carbon Nanofibers and NanotubesADVANCED FUNCTIONAL MATERIALS, Issue 8 2009Tamara Druzhinina Abstract The fast and cheap synthesis of carbon nanotubes is addressed in a large number of recent publications. At the same time, microwave-assisted synthesis has also gained interest. Besides the fact that reaction kinetics can be positively influenced by the use of microwave irradiation and advanced reaction conditions can be applied, absorption of microwave radiation depends on the material properties, thus resulting in a selective heating mechanism. The selective heating process allows for locally created temperatures high enough to promote the growth of carbon nanofibers and nanotubes on patterned iron catalyst layers. The resulting fibers are micrometers long, and can be synthesized in short time scales of a few minutes, yielding dense films of carbon fibers with uniform height. Here, the selective heating of surface bound iron nanoparticles is investigated in more detail, and experimental evidence for this effect is provided by utilizing a self-assembled monolayer of n -octadecyltrichlorosilane, which acts as a sensitive indicator for locally elevated temperatures. Special emphasis is placed on the development of an improved and controllable experimental setup that permits the safe and fast fabrication of the desired carbon objects. [source] Effects of Mixing Granular Iron with Sand on the Kinetics of Trichloroethylene ReductionGROUND WATER MONITORING & REMEDIATION, Issue 2 2009Erping Bi A substantial cost of granular iron permeable reactive barriers is that of the granular iron itself. Cutting the iron with sand can reduce costs, but several performance issues arise. In particular, reaction rates are expected to decline as the percentage of iron in the blend is diminished. This might occur simply as a function of iron content, or mass transfer effects may play a role in a much less predictable fashion. Column experiments were conducted to investigate the performance consequences of mixing Connelly granular iron with sand using the reduction kinetics of trichloroethylene (TCE) to quantify the changes. Five mixing ratios (i.e., 100%, 85%, 75%, 50%, and 25% of iron by weight) were studied. The experimental data showed that there is a noticeable decrease in the reaction rate when the content of sand is 25% by weight (iron mass to pore volume ratio, Fe/Vp = 3548 g/L) or greater. An analysis of the reaction kinetics, using the Langmuir-Hinshelwood rate equation, indicated that mass transfer became an apparent cause of rate loss when the iron content fell below 50% by weight (Fe/Vp = 2223 g/L). Paradoxically, there were tentative indications that TCE removal rates were higher in a 15% sand + 85% iron mixture (Fe/Vp = 4416 g/L) than they were in 100% iron (Fe/Vp = 4577 g/L). This subtle improvement in performance might be due to an increase of iron surface available for contact with TCE, due to grain packing in the sand-iron mixture. [source] Treatment of a Chromate-Contaminated Soil Site by in situ Gaseous ReductionGROUND WATER MONITORING & REMEDIATION, Issue 1 2007E.C Thornton A proof-of-concept field test for the treatment of hexavalent chromium in the vadose zone using in situ gaseous reduction was successfully completed by the U.S. Department of Energy and U.S. Department of Defense in a joint demonstration conducted at White Sands Missile Range, New Mexico. The test involved injecting hydrogen sulfide, diluted in air, into contaminated vadose zone sediment to reduce Cr(VI) to Cr(III). The gaseous mixture was injected directly into the contaminated sediment through a central injection well and vacuum extracted through the flow field with six boreholes at the site periphery over a 76-d period. Comparison of soil samples taken before and after the test indicated 70% of the total mass of hexavalent chromium originally present at the site was reduced and immobilized. The zone of highest contamination was nearly completely treated, with average Cr(VI) concentrations decreasing in this interval from an average of 8.1 mg/kg before treatment to 1.1 mg/kg after treatment. Treatment was best in higher permeability clean gypsum sands and less effective in zones containing greater amounts of silt and clay and a slightly higher iron content. All hexavalent chromium concentrations measured in the posttest samples, however, were well below the remedial goal and regulatory limit of 30 mg/kg. In addition, the field test demonstrated that vadose zone treatment of contamination can be safely conducted using diluted hydrogen sulfide gas mixtures. Ongoing development of the technology is being directed toward addressing the limitations of gaseous treatment arising from variations in sediment permeability and iron content and assessing the relationship between hydrogen sulfide consumption and reaction kinetics. [source] Kinetic studies of hydrazine and 2-hydroxyethylhydrazine alkylation by 2-chloroethanol: Influence of a strong base in the mediumINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2009V. Goutelle To optimize yields, the study of reaction kinetics related to the synthesis of 2-hydroxyethylhydrazine (HEH) obtained from the alkylation of N2H4 by 2-chloroethanol (CletOH) was carried out with and without sodium hydroxide. In both cases, the main reaction of HEH formation was followed by a consecutive, parallel reaction of HEH alkylation (or dialkylation of N2H4), leading to the formation of two isomers: 1,1-di(hydroxyethyl)hydrazine and 1,2-di(hydroxyethyl)hydrazine. In this study, hydrazine and hydroxyalkylhydrazine alkylations followed SN2 reactions triggered directly by CletOH or indirectly in the presence of a strong base by ethylene oxide, an intermediate compound. The kinetics was studied in diluted mediums by quantifying HEH and CletOH by gas chromatography and gas chromatography coupled with mass spectrometry (GC-MS). The activation parameters of each reaction and the influence of a strong base present in the medium on the reaction mechanisms were established. A global mathematical treatment was applied for each alternative. It allowed modeling the reactions as a function of reagent concentrations and temperature. In the case of direct alkylation by CletOH, simulation was established for semi-batch and batch syntheses and was confirmed in experiments for concentrated mediums (1.0 M , [CletOH]0 , 3.2 M and 15.7 M , [N2H4]0 , 18.8 M). Simulation therefore permits the prediction of the instantaneous concentration of reagents and products, in particular ethylene oxide concentration in the case of indirect alkylation, which must be as weak as possible. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 382,393, 2009 [source] Kinetic study of transesterification of methyl acetate with n -butanol catalyzed by NKC-9INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2009Baoyun Xu The transesterification of methyl acetate and n -butanol catalyzed by cation-exchange resin, NKC-9, was studied in this work to obtain the reaction kinetics. The experiments were carried out in a stirred batch reactor at different temperatures (328.15, 333.15, 338.15, 343.15, 345.15 K) under atmospheric pressure. The effects of temperature, molar ratio of reactants, and catalyst loading on the reaction rate were researched under the condition of eliminating the effect of diffusion. The experimental data were correlated with a kinetic model based on the pseudo-homogeneous catalysis. The kinetic equation describing the reaction catalyzed by NKC-9 was developed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 101,106, 2009 [source] Preparation and thermal decomposition reaction kinetics of a dysprosium(III) p -chlorobenzoate 1,10-phenanthroline complexINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2008Jian Jun Zhang The title complex [Dy(p -ClBA)3Phen]2·2H2O was synthesized, where p -ClBA is p -chlorobenzoate and Phen is 1,10-phenanthroline. The complex was characterized by various techniques including elemental analysis, IR, XRD, and molar conductance. The thermal decomposition of the complex was studied under the nonisothermal condition by TG-DTG and IR techniques. The kinetic parameters of dehydration process were obtained from the analysis of DSC curves of the complex by the NL-DIF and Popescu methods, respectively. © 2007 Wiley Periodicals, Inc. 40: 66,72, 2008 [source] The kinetics of complex formation between Ti(IV) and hydrogen peroxideINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2007Daniel W. O'Sullivan The kinetics of the formation of the titanium-peroxide [TiO2+2] complex from the reaction of Ti(IV)OSO4 with hydrogen peroxide and the hydrolysis of hydroxymethyl hydroperoxide (HMHP) were examined to determine whether Ti(IV)OSO4 could be used to distinguish between hydrogen peroxide and HMHP in mixed solutions. Stopped-flow analysis coupled to UV-vis spectroscopy was used to examine the reaction kinetics at various temperatures. The molar absorptivity (,) of the [TiO2+2] complex was found to be 679.5 ± 20.8 L mol,1 cm,1 at 405 nm. The reaction between hydrogen peroxide and Ti(IV)OSO4 was first order with respect to both Ti(IV)OSO4 and H2O2 with a rate constant of 5.70 ± 0.18 × 104 M,1 s,1 at 25°C, and an activation energy, Ea = 40.5 ± 1.9 kJ mol,1. The rate constant for the hydrolysis of HMHP was 4.3 × 10,3 s,1 at pH 8.5. Since the rate of complex formation between Ti(IV)OSO4 and hydrogen peroxide is much faster than the rate of hydrolysis of HMHP, the Ti(IV)OSO4 reaction coupled to time-dependent UV-vis spectroscopic measurements can be used to distinguish between hydrogen peroxide and HMHP in solution. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 457,461, 2007 [source] Synthesis and thermal decomposition reaction kinetics of complexes of [Sm2(m -ClBA)6(phen)2],·,2H2O and [Sm2(m -BrBA)6(phen)2],·,2H2OINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2007Jian Jun Zhang Complexes of [Sm2(m -ClBA)6(phen)2],·,2H2O and [Sm2(m -BrBA)6(phen)2],·,2H2O (m -ClBA = m -chlorobenzoate, m -BrBA = m -bromobenzoate, and phen = 1,10-phenanthroline) were prepared and characterized by elemental analysis and IR spectra. The thermal decomposition processes of the two complexes were studied by means of TG,DTG and IR techniques. Their thermal decomposition kinetics were investigated from the analysis of the TG and DTG curves by jointly using a new method proposed by us and a newly nonlinear isoconversional integral method. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 67,74, 2007 [source] Effect of surfactant micelles on the kinetics of oxidation of D -fructose by cerium(IV) in sulfuric acid mediumINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2006Kabir-ud-Din Kinetics of the oxidation of D -fructose by cerium(IV) has been investigated both in the absence and presence of surfactants (cetyltrimethylammonium bromide, CTAB, and sodium dodecyl sulfate, SDS) in sulfuric acid medium. The reaction exhibits first-order kinetics each in [cerium(IV)] and [D -fructose] and inverse first order in [H2SO4]. The Arrhenius equation is found to be valid for the reaction between 30,50°C. A detailed mechanism with the associated reaction kinetics is presented and discussed. While SDS has no effect, CTAB increases the reaction rate with the same kinetic behavior in its presence. The catalytic role of CTAB micelles is discussed in terms of the pseudophase model proposed by Menger and Portnoy. The association constant Ks that equals to 286 mol,1 dm3 is found for the association of cerium(IV) with the positive head group of CTAB micelles. The effect of inorganic electrolytes (Na2SO4, NaNO3, NaCl) has also been studied and discussed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 18,25, 2006 [source] Reaction of 4-benzylidene-2-methyl-5-oxazolone with amines, Part 2: Influence of substituents in para-position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kineticsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2002B. Bet, akowska An influence of a structure of the amine (benzylamine, N -methyl-benzylamine, N -isopropyl-benzylamine, N -methyl-butylamine, N -ethyl-butylamine, sec -butylamine, and tert -butylamine) on a rate constant of the ring-opening reaction of 4-benzylidene-2-methyl-5-oxazolone (Ox) was studied. The good correlation between logarithm of the rate constants and Charton's steric substituent constant , as well as good correlation with a form of the simple branching equation indicate that there is a steric effect because of substitution at C1 carbon atom of nucleophile which decreases the reaction rate. Additionally, an influence of a structure of the benzylidene moiety of Ox on a rate of the oxazolone ring-opening reaction was studied. The substituents (OH, OCH3, N(CH3)2, Cl, NO2) in para-position of the phenyl ring of Ox substantially modified the rate of the reaction with benzylamine in acetonitrile. The rate of the Ox ring-opening reaction decreased with increase of the electron-donating properties of the substituent. A good correlation between the rate constants of the reaction of 4-(4,-substituted-benzylidene)-2-methyl-5-oxazolones with benzylamine and the electron density at the reaction center (carbon C5 of the oxazolone ring), calculated using ab initio method, and the Hammett substituent constants, and CR equation were established. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 148,155, 2002; DOI 10.1002/kin.10039 [source] Theoretical study of the · H reaction with cytosineINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2007Hongyu Zhang Abstract We studied three possible reactions of H atom attacking the cytosine, using density functional theory (DFT) calculations. The results indicate that the H atom addition to the N3 site of cytosine is energetically more favorable than to the C5 or C6 site. The reaction of addition to the C6 site has an energy barrier of ,2.77 kcal/mol, which is ,2 kcal/mol higher than addition to C5. The energy of C5 H-adduct radical is also lower than that of C6 H-adduct radical. From the point of view of both energetics and reaction kinetics, the addition of the H atom to the C5 site is preferred to the addition to the C6 site. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] | ||||||||||||||||||||||||||||||||||||||||||||||