Home About us Contact
|
Home About us Contact | ||
|
|
||
Coefficient K (coefficient + k)
Selected AbstractsThe reaction between ethyl and molecular oxygen II: Further analysisINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2001James A. Miller The present investigation is a rather substantial extension and elaboration of our previous work on the same reaction. In this article we accomplish four primary objectives: 1.We show quantitatively how sensitive the high-temperature rate coefficient k(T) is to E02, the threshold energy of the transition state for direct molecular elimination of HO2 from ethylperoxy radical (C2H5O2), thus deducing a value of E02=,3.0 kcal/mol (measured from reactants). 2.We derive the result that k0(T) , k,,(T) in the high-temperature regime, where k0(T) is the zero-pressure rate coefficient, and k,,(T) is the infinite-pressure rate coefficient for the bimolecular channel. 3.Most importantly, we discuss the three different regimes of the reaction (low-temperature, transition, and high-temperature) in terms of the eigenvectors and eigenvalues of G, the transition matrix of the master equation. The transition regime is shown to be a region of avoided crossing between the two chemically significant eigenvalue curves in which the thermal rate coefficient k (T ,p) jumps from one eigenvalue to the other. This jump is accompanied by a "mixing" of the corresponding eigenvectors, through which both eigenvectors deplete the reactant. The onset of the high-temperature regime is triggered by reaching the "stabilization limit" of the ethylperoxy adduct, a limit that is induced by a shift in equilibrium of the stabilization reaction. Our identification of the prompt and secondary HO2 formed by the reaction with these eigenvalue/eigenvector pairs leads to good agreement between theory and the experiments of Clifford et al. (J Phys Chem A 2000, 104, 11549,11560). 4.Lastly, we describe the master equation results in terms of a set of elementary reactions and phenomenological rate coefficients. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 732,740, 2001 [source] EPR Analysis of n -Butyl Acrylate Radical PolymerizationMACROMOLECULAR RAPID COMMUNICATIONS, Issue 23 2009Johannes Barth Abstract Via electron paramagnetic resonance (EPR) spectroscopy, concentrations of secondary propagating radicals (SPRs) and tertiary mid-chain radicals (MCRs) in n -butyl acrylate solution polymerization were measured. The EPR spectrum is dominated by the 4-line spectrum of SPRs at ,50,°C and by the 7-line spectrum of MCRs at +70,°C. At intermediate temperatures, a third spectral component is seen, which is assigned to an MCR species with restricted rotational mobility. The MCR components are produced by 1,5-hydrogen shift (backbiting) of SPRs. The measured ratio of MCRs to SPRs allows for estimating the rate coefficient k for monomer addition to a mid-chain radical. For 70,°C, k is obtained to be 65.5 L,·,mol,1,·,s,1. [source] Semigroup approach for identification of the unknown diffusion coefficient in a quasi-linear parabolic equationMATHEMATICAL METHODS IN THE APPLIED SCIENCES, Issue 11 2007Ali Demir Abstract This article presents a semigroup approach for the mathematical analysis of the inverse coefficient problems of identifying the unknown coefficient k(u(x,t)) in the quasi-linear parabolic equation ut(x,t)=(k(u(x,t))ux(x,t))x, with Dirichlet boundary conditions u(0,t)=,0, u(1,t)=,1. The main purpose of this paper is to investigate the distinguishability of the input,output mappings ,[,]:,, ,C1[0,T], ,[,]:,,,C1[0,T] via semigroup theory. In this paper, it is shown that if the null space of the semigroup T(t) consists of only zero function, then the input,output mappings ,[,] and ,[,] have the distinguishability property. It is also shown that the types of the boundary conditions and the region on which the problem is defined play an important role in the distinguishability property of these mappings. Moreover, under the light of measured output data (boundary observations) f(t):=k(u(0,t))ux(0,t) or/and h(t):=k(u(1,t))ux(1,t), the values k(,0) and k(,1) of the unknown diffusion coefficient k(u(x,t)) at (x,t)=(0,0) and (x,t)=(1,0), respectively, can be determined explicitly. In addition to these, the values ku(,0) and ku(,1) of the unknown coefficient k(u(x,t)) at (x,t)=(0,0) and (x,t)=(1,0), respectively, are also determined via the input data. Furthermore, it is shown that measured output dataf(t) and h(t) can be determined analytically by an integral representation. Hence the input,output mappings ,[,]:,,, C1[0,T], ,[,]:,,,C1[0,T] are given explicitly in terms of the semigroup. Copyright © 2007 John Wiley & Sons, Ltd. [source] Chronic lithium administration attenuates up-regulated brain arachidonic acid metabolism in a rat model of neuroinflammationJOURNAL OF NEUROCHEMISTRY, Issue 3 2007Mireille Basselin Abstract Neuroinflammation, caused by a 6-day intracerebroventricular infusion of lipopolysaccharide (LPS) in rats, is associated with the up-regulation of brain arachidonic acid (AA) metabolism markers. Because chronic LiCl down-regulates markers of brain AA metabolism, we hypothesized that it would attenuate increments of these markers in LPS-infused rats. Incorporation coefficients k* of AA from plasma into brain, and other brain AA metabolic markers, were measured in rats that had been fed a LiCl or control diet for 6 weeks, and subjected in the last 6 days on the diet to intracerebroventricular infusion of artificial CSF or of LPS. In rats on the control diet, LPS compared with CSF infusion increased k* significantly in 28 regions, whereas the LiCl diet prevented k* increments in 18 of these regions. LiCl in CSF infused rats increased k* in 14 regions, largely belonging to auditory and visual systems. Brain cytoplasmic phospholipase A2 activity, and prostaglandin E2 and thromboxane B2 concentrations, were increased significantly by LPS infusion in rats fed the control but not the LiCl diet. Chronic LiCl administration attenuates LPS-induced up-regulation of a number of brain AA metabolism markers. To the extent that this up-regulation has neuropathological consequences, lithium might be considered for treating human brain diseases accompanied by neuroinflammation. [source] Modelling of air drying of Hac,haliloglu-type apricotsJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 2 2006Hakan Okyay Menges Abstract In this study a laboratory dryer was used for the thin layer drying of sulfured and non-sulfured apricots. The moisture ratio values throughout the drying process were calculated by 14 different mathematical models, namely Newton, Page, modified Page, modified Page-II, Henderson and Pabis, logarithmic, two-term, two-term exponential, Wang and Singh, Thompson, diffusion approximation, modified Henderson and Papis, Verma et al. and Midilli et al. models. Root mean square error, reduced chi-square, mean bias error, adjusted R -square and modelling efficiency were used as statistical parameters to determine the most suitable model among them. According to the results, the Page model was chosen to explain the thin layer drying behaviour of sulfured and non-sulfured apricots. The effects of drying air temperature (T) and velocity (V) on the constants and coefficients of the best moisture ratio model were determined by multiple regression analysis. The moisture ratio (MR) could be predicted by the Page model equation MR = exp(,ktn) with constants and coefficients k = 0.470893 + 0.078775V and n = 0.017786 exp(0.051935T) for sulfured apricots and k = 4.578252 + 1.144643T and n = 0.888040 + 0.145559V for non-sulfured apricots. It is possible to predict the moisture content of the product with the generalised Page model incorporating the effects of drying air temperature and velocity on the model constants and coefficients in the ranges T = 70,80 °C and V = 1,3 m s,1. This developed model showed acceptable agreement with the experimental results, explained the drying behaviour of the product and could also be used for engineering applications. Copyright © 2005 Society of Chemical Industry [source] Structural, electronic and optical calculations of Cu(In,Ga)Se2 ternary chalcopyritesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2004M. Belhadj Abstract In this work, we have investigated the structural, electronic and optical properties of the ternary I,III,VI2 chalcopyrite semiconductors ABX2 (A = Cu, B = In, Ga, X = Se) by means of a first-principles density-functional total-energy calculation with the local-density approximation (LDA), using the all-electron full-potential linear-augmented plane-wave method (FP-LAPW). The equilibrium lattice constants and the bulk moduli (a, c, c/a, u and B0) are compared with other theoretical calculations. The energy gap at ambient pressure is found to be direct and the nature of the gap crucially depends on the manner in which the d electrons of the A atoms are treated. We have also reported the optical properties of two chalcopyrite semiconductors CuInSe2 and CuGaSe2. Results on complex dielectric functions, refractive indices n, extinction coefficients k, and normal-incidence reflectivity R in the two crystals are given and compared with earlier data where available. We analyze in detail the structures of the dielectric function observed in the studied energy region. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] | ||||||||||