Kinetic Results (kinetic + result)

Distribution by Scientific Domains

Selected Abstracts

An experimental and modeling study of Na-rich hydrothermal alteration

Abstract Sodic alteration assemblages including clinoptilolite, mordenite, analcime and Na-montmorillonite were locally observed in sediments in the eastern part of the Hachimantai geothermal region, northeast Japan. This study investigated the mechanisms of sodic enrichment in the sediments during alteration. Kinetic results for water/rock interaction experiments are reported here. Batch-type experiments were conducted at 150,250°C under saturated vapor pressure. Pyroclastic rocks dissolved incongruently in these experiments, and the solubility and dissolution rates among elements varied as follows: the apparent steady-state concentrations of major elements are Si > Na , K > Ca > Al and the order of the dissolution rates is Si > Al > Na , K > Ca. Na had the highest steady-state concentration and fastest dissolution rate of the alkali and alkali earth metal ions. Based on surface analysis of plagioclase, dissolution was effected via a reaction layer of Na-montmorillonite on the mineral surface. Additionally, a reaction model constructed based on the experimentally observed reaction mechanism quantitatively explains the dissolution behavior. These results show that Na-montmorillonite can be precipitated by pyroclastic rock/meteoric water interactions without seawater involvement: the Na is derived from the host rocks. [source]

Kinetics of (Porphyrin)manganese(III)-Catalyzed Olefin Epoxidation with a Soluble Iodosylbenzene Derivative

James P. Collman
Abstract We examined the kinetics of a well-behaved system for homogeneous porphyrin-catalyzed olefin epoxidation with a soluble iodosylbenzene derivative 1 as the terminal oxidant and Mn(TPFPP)Cl (2) as the catalyst. The epoxidation rates were measured by using the initial rate method, and the epoxidation products were determined by gas chromatography. The epoxidation rate was found to be first order with respect to the porphyrin catalyst and zero order on the terminal oxidant. In addition, we found the rate law to be sensitive to the nature and concentration of olefin substrates. Saturation kinetics were observed with all olefin substrates at high olefin concentrations, and the kinetic data are consistent with a Michaelis,Menten kinetic model. According to the observed saturation kinetic results, we propose that there is a complexation between the active oxidant and the substrate, and the rate-determining step is thought to be the breakdown of this putative substrate,oxidant complex that generates the epoxidation products and the resting state porphyrin catalyst. Competitive epoxidations further indicate a reversible complexation of the active oxidant and the olefin substrate. The activation parameters ,H, and ,S, for the oxygen-transfer process (k2) in the cis -cyclooctene epoxidation were determined to be 12.3,±,0.9 kcal,mol,1 and,15.6,±,3.2 cal,mol,1,K,1, respectively. In addition, the Hammett constant ,+ was measured for the epoxidation of para -substituted styrenes, and the value of ,0.27,±,0.04 is too low to be consistent with the involvement of a discrete carbocation in the transition state. We also prepared a (porphyrin)manganese catalyst immobilized on silica support, and found the epoxidation of cis -cyclooctene catalyzed by this heterogeneous catalyst proceeds at virtually the same turnover frequency as by the homogeneous porphyrin catalyst. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Solvent and structural effects on the kinetics of the reactions of 2-substituted cyclohex-1-enylcarboxylic and 2-substituted benzoic acids with diazodiphenylmethane

J. B. Nikoli
The rate constants for the reaction of 2-methyl-cyclohex-1-enylcarboxylic, 2-phenylcyclohex-1-enylcarboxylic, and 2-methylbenzoic and 2-phenylbenzoic acids with diazodiphenyl-methane were determined in 14 various solvents at 30°C. To explain the kinetic results through solvent effects, the second-order rate constants of the examined acids were correlated using the Kamlet,Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The quantitative relationship between the molecular structure and the chemical reactivity has been discussed, as well as the effect of geometry on the reactivity of the examined molecules. The geometric data of all the examined compounds corresponding to the energy minima in solvent, simulated as dielectric continuum, obtained using semiempirical MNDO-PM3 energy calculations. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 664,671, 2007 [source]

Theoretical studies on farnesyl transferase: Evidence for thioether product coordination to the active-site zinc sphere

Sérgio Filipe Sousa
Abstract Farnesyltransferase (FTase), an interesting zinc metaloenzyme, has been the subject of great attention in anticancer research over the last decade. However, despite the major accomplishments in the field, some very pungent questions on the farnesylation mechanism still persist. In this study, the authors have analyzed a mechanistic paradox that arises from the existence of several contradicting and inconclusive experimental evidence regarding the existence of direct coordination between the active-site zinc cation and the thioether from the farnesylated peptide product, which include UV,vis spectroscopy data on a Co2+ -substituted FTase, two X-ray crystallographic structures of the FTase-product complex, and extended X-ray absorption fine structure results. Using high-level theoretical calculations on two models of different sizes, and QM/MM calculations on the full enzyme, the authors have shown that the farnesylated product is Zn coordinated, and that a subsequent step where this Zn bond is broken is coherent with the available kinetic results. Furthermore, an explanation for the contradicting experimental evidence is suggested. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source]

Kinetics of separating multicomponent mixtures by nondispersive solvent extraction: Ni and Cd

AICHE JOURNAL, Issue 4 2001
Inmaculada Ortiz
A model for nonsteady metals separation using nondispersive solvent extraction presented explicitly accounts for selective separation of multicomponent solutions and concentration of separated components in a back-extraction phase. The separation process comprises extraction and back-extraction steps carried out in two different hollow-fiber modules, connected through the organic phase, together with three homogenization tanks. The model is based on a set of coupled differential equations describing mass balances of metallic solutes in the fluid phases. To be applied in its simplest form, it requires the knowledge of three characteristic parameters, two parameters related to the chemical reactions, and one mass-transport parameter. The latter describes the mass-transport rate through pores of the hollow-fiber membrane filled with the organic phase. The mathematical model was checked against the kinetic results of the separation of Cd/Ni mixtures working with high-concentration solutions and obtaining the characteristic parameters of this system. [source]

Basics and applications of solid-state kinetics: A pharmaceutical perspective,

Ammar Khawam
Abstract Most solid-state kinetic principles were derived from those for homogenous phases in the past century. Rate laws describing solid-state degradation are more complex than those in homogenous phases. Solid-state kinetic reactions can be mechanistically classified as nucleation, geometrical contraction, diffusion, and reaction order models. Experimentally, solid-state kinetics is studied either isothermally or nonisothermally. Many mathematical methods have been developed to interpret experimental data for both heating protocols. These methods generally fall into one of two categories: model-fitting and model-free. Controversies have arisen with regard to interpreting solid-state kinetic results, which include variable activation energy, calculation methods, and kinetic compensation effects. Solid-state kinetic studies have appeared in the pharmaceutical literature over many years; some of the more recent ones are discussed in this review. © 2006 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 95:472,498, 2006 [source]

Tunnelling corrections in hydrogen abstractions by excited-state ketones

Monica Barroso
Abstract Hydrogen abstraction from 1-phenylethanol by triplet acetophenone occurs from both CH and OH bonds. The reaction path of the Interacting-State Model (ISM) is used with the Transition-State Theory (TST) and the semiclassical correction for tunnelling (ISM/scTST) to help rationalizing the experimental kinetic results and elucidate the mechanisms of these reactions. The weak exothermicity of the abstraction from the strong OH bond is compensated by electronic effects, hydrogen bonding and tunnelling, and is competitive with the more exothermic abstraction from the ,-CH bond of 1-phenylethanol. The alkoxy radical formed upon abstraction from OH reacts within the solvent cage and the primary product of this reaction is 1-phenylethenol. The corresponding kinetic isotope effect is ca. 3 and is entirely consistent with a tunnelling correction ca. 9 for H abstraction. We therefore demonstrate that the tunnelling correction is the major contributor to the kinetic isotope effect. Copyright © 2010 John Wiley & Sons, Ltd. [source]

Non-aqueous reverse micelles media for the SNAr reaction between 1-fluoro-2,4-dinitrobenzene and piperidine,

N. Mariano Correa
Abstract The kinetics of the nucleophilic aromatic substitution (SNAr) reaction between 1-fluoro-2,4- dinitrobenzene (FDNB) and piperidine (PIP) in ethylene glycol (EG)/ sodium bis (2-ethyl-1-hexyl) sulfosuccinate (AOT)/n -heptane and dimethylformamide (DMF)/AOT/n -heptane non-aqueous reverse micelle systems is reported. EG and DMF were used as models for hydrogen bond donor (HBD) and non-hydrogen bond donor (non-HBD) polar solvents, respectively. The reaction was found not to be base catalyzed in these media. A mechanism to rationalize the kinetic results is proposed in which both reactants may be distributed between the two environments. The distribution constants of FDNB between the organic and each micellar pseudophases were determined by an independent fluorescence method. These results were used to evaluate the amine distribution constant and the intrinsic second-order rate coefficient of the SNAr reaction in the interface. The reaction was also studied in the pure solvents EG and DMF for comparison. The results in EG/AOT/n -heptane at Ws,=,2 give similar kinetic profiles than in water/AOT/n -hexane at W,=,10. With these HBD solvents, the interface saturation by the substrate is reached at around the same value of [AOT] and the intrinsic second-order rate coefficient in the interface, k,b, has comparable values. On the other hand, when DMF is used as a polar non-HBD solvent, the intrinsic second-order rate constant increases by a factor of about 200 as compared to the values obtained using HBD solvents as a polar core. It is concluded that higher catalytic power is obtained when non-HBD solvents are used as polar solvent in the micelle interior. Copyright © 2006 John Wiley & Sons, Ltd. [source]

The Effect of Confined Space on the Growth of Naphthalenic Species in a Chabazite-Type Catalyst: A Molecular Modeling Study

CHEMCATCHEM, Issue 3 2009
Karen Hemelsoet Dr.
Abstract Methylation reactions of naphthalenic species over the acidic microporous zeolite with chabazite topology have been investigated by means of two-layered ab,initio computations. Large cluster results combined with van,der Waals contributions provide thermodynamic and kinetic results of successive methylation steps. The growth of fused bicyclic species is important as these can act as hydrocarbon pool species within the methanol-to-olefin (MTO) process, but ultimately leads to the deactivation of the catalyst. The influence of the confined space of the zeolite pore on the resulting transition state or product shape selectivity is investigated in detail. [source]