Kinetic Reactions (kinetic + reaction)

Distribution by Scientific Domains

Selected Abstracts

Curing kinetics of boron-containing phenol,formaldehyde resin formed from paraformaldehyde

Yanfang Liu
A boron-containing phenol,formaldehyde resin (BPFR) was synthesized from boric acid, phenol, and paraformaldehyde. The curing reaction of BPFR was studied by Fourier-transform infrared spectrometry and differential scanning calorimetry. According to the heat evolution behavior during the curing process, several influencing factors on isothermal curing reaction were evaluated. The results show that the isothermal kinetic reaction of BPFR follows autocatalytic kinetics mechanism, and kinetic parameters m, n, k1, and k2, were derived, respectively. In the latter reaction stage, the curing reaction becomes controlled mainly by diffusion. 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 638,644, 2002 [source]

Determination of the 2,3-pentadienedioic acid enantiomer interconversion energy barrier 1.

Classical kinetic approach
Abstract A classical kinetic method was used to determine the energy barrier for the interconversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+) , (,) and (,) , (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a first-order kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (,G# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22C (,Gapp = 93.9 0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i. e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition. [source]

Behaviour modelling of a PEMFC operating on diluted hydrogen feed

M. Minutillo
Abstract The polymer electrolyte membrane fuel cell (PEMFC) using reformate gas as fuel is regarded as an attractive solution for the near-term introduction of fuel cells in stationary or mobile power generation market. With respect to hydrogen feeding, the reformate gas fuelling involves additional polarization losses because of the hydrogen dilution and the impurities contained in the gas. In this paper a one-dimensional model has been developed to investigate the behaviour of a PEMFC operating with reformate gas mixture. The model, based on a semi-empirical approach, considers the kinetic reactions in the anode side taking into account the effect of reverse water,gas shift (RWGS) due to the presence of CO2 in the fuel. As it is well known, the exhaust stream from fuel reformers can contain a high carbon dioxide concentration (>20%) that can have a detrimental effect on the fuel cell performance because of the combination of the dilution and the formation of CO by the RWGS reaction. The numerical simulation results have been compared with the experimental data, obtained in the test room of Industrial Engineering Department of Cassino University, and a good match has been observed. The model has been developed by using a simplified approach that, nevertheless, can allow to obtain a good numerical prediction of the fuel cell performance reducing the simulation time and computational efforts. Copyright 2008 John Wiley & Sons, Ltd. [source]

On the use of large time steps with ELLAM for transport with kinetic reactions over heterogeneous domains

AICHE JOURNAL, Issue 5 2009
Marwan Fahs
Abstract An Eulerian Lagrangian localized adjoint method (ELLAM) is considered for the resolution of advection-dominated transport problems in porous media. Contrary to standard Eulerian methods, ELLAM can use large time steps because the advection term is approximated accurately without any CFL restriction. However, it is shown in this article that special care must be taken for the approximation of the dispersive and reactive terms when large time steps are used over heterogeneous domains. An alternative procedure is proposed. It is based on an equivalent dispersion coefficient or an equivalent reaction rate when different zones are encountered during the tracking. Numerical experiments are performed with variable dispersion or variable reaction rates over space (including nonlinearity). When classical ELLAM require numerous time steps to handle heterogeneity, the alternative procedure is shown to perform with the same accuracy in a single time step. 2009 American Institute of Chemical Engineers AIChE J, 2009 [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]