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Collision Theory (collision + theory)
Selected AbstractsKinetics of the gas-phase reactions of cyclo-CF2CFXCHXCHX , (X = H, F, Cl) with OH radicals at 253,328 KINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2009L. Chen Rate constants were determined for the reactions of OH radicals with halogenated cyclobutanes cyclo-CF2CF2CHFCH2(k1), trans -cyclo-CF2CF2CHClCHF(k2), cyclo-CF2CFClCH2CH2(k3), trans -cyclo-CF2CFClCHClCH2(k4), and cis -cyclo-CF2CFClCHClCH2(k5) by using a relative rate method. OH radicals were prepared by photolysis of ozone at a UV wavelength (254 nm) in 200 Torr of a sample reference H2OO3O2He gas mixture in an 11.5-dm3 temperature-controlled reaction chamber. Rate constants of k1 = (5.52 ± 1.32) × 10,13 exp[,(1050 ± 70)/T], k2 = (3.37 ± 0.88) × 10,13 exp[,(850 ± 80)/T], k3 = (9.54 ± 4.34) × 10,13 exp[,(1000 ± 140)/T], k4 = (5.47 ± 0.90) × 10,13 exp[,(720 ± 50)/T], and k5 = (5.21 ± 0.88) × 10,13 exp[,(630 ± 50)/T] cm3 molecule,1 s,1 were obtained at 253,328 K. The errors reported are ± 2 standard deviations, and represent precision only. Potential systematic errors associated with uncertainties in the reference rate constants could add an additional 10%,15% uncertainty to the uncertainty of k1,k5. The reactivity trends of these OH radical reactions were analyzed by using a collision theory,based kinetic equation. The rate constants k1,k5 as well as those of related halogenated cyclobutane analogues were found to be strongly correlated with their CH bond dissociation enthalpies. We consider the dominant tropospheric loss process for the halogenated cyclobutanes studied here to be by reaction with the OH radicals, and atmospheric lifetimes of 3.2, 2.5, 1.5, 0.9, and 0.7 years are calculated for cyclo-CF2CF2CHFCH2, trans -cyclo-CF2CF2CHClCHF, cyclo-CF2CFClCH2CH2, trans -cyclo-CF2CFClCHClCH2, and cis -cyclo-CF2CFClCHClCH2, respectively, by scaling from the lifetime of CH3CCl3. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 532,542, 2009 [source] Reactions of gaseous ions.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2001Editor's Note: The following paper is the first in a series that describes the gas phase reactions of positive ions derived from compounds such as methane and ethylene with other gas phase molecules to produce secondary ions. These very careful experiments formed the basis of chemical ionization, one of the ionization techniques that revolutionized mass spectrometry at that time and a technique still very much in use today. At elevated pressures in a mass spectrometer ion source reactions occur between certain ions and the neutral species present. We have studied the various secondary ions formed in methane and ethylene at elevated pressures and have determined the reactions by which they are formed and the rates of these reactions. The rates are all extremely fast. The reaction rates have been treated by classical collision theory and it has been shown that to a fair approximation the cross-sections and reaction rate constants can be predicted from a simple balance of rotational and polarization forces. [Reprinted from J. Am. Chem. Soc. 1957; 79: 2419.] Copyright © 1957 by the American Chemical Society and reprinted by permission of the copyright owner. [source] SCT reaction kinetics model and diffusion for p.c. combustion in TGAASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 2 2010Pei-Fang Fu Abstract Recently, the process of char burnout is extensively concerned. Global model used widely cannot predict the extent of char burnout at the later burning stage. For the need of predicting the burnout degree in industrial pulverized coal (p.c.) fired furnace by making use of the experimental data from such as thermogravimetry analysis (TGA) and drop tube furnace, based on the simple collision theory (SCT) of chemical reaction kinetics, the SCT model is educed. The p.c. combustion is considered as the results of strike and oxidation of oxygen molecules on the surface of p.c. particles, and the frequency of effective strike was determined by Boltzmann factor. Strike and oxidation occur on the oxygen accessible specific surface area (OASA). Chemical regime controlled is at temperature below 1200 K, and molecules diffusion regime controlled is at the temperature above 1600 K, at which OASA corresponds to the specific surface area with pore diameter more than 38 nm of p.c particles in coal-fired boiler. The OASA of p.c. particles increases with the char burning, for the particles swells, shrinks and cracks. The burning rates calculated based on SCT model have shown good correspondence with experimental data reported. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Catalytic behaviors of enzymes attached to nanoparticles: the effect of particle mobilityBIOTECHNOLOGY & BIOENGINEERING, Issue 4 2003Hongfei Jia Abstract Nanoparticles provide an ideal remedy to the usually contradictory issues encountered in the optimization of immobilized enzymes: minimum diffusional limitation, maximum surface area per unit mass, and high effective enzyme loading. In addition to the promising performance features, the unique solution behaviors of the nanoparticles also point to a transitional region between the heterogeneous (with immobilized enzymes) and homogeneous (with soluble free enzymes) catalysis. The particle mobility, which is related to particle size and solution viscosity through Stokes-Einstein equation, may impact the reaction kinetics according to the collision theory. The mobility-activity relationship was examined through experimental studies and theoretical modeling in the present work. Polystyrene particles with diameters ranging from 110,1000 nm were prepared. A model enzyme, ,-chymotrypsin, was covalently attached to the nanoparticles up to 6.6 wt%. The collision theory model was found feasible in correlating the catalytic activities of particles to particle size and solution viscosity. Changes in the size of particles and the viscosity of reaction media, which all affect the mobility of the enzyme catalyst, evidently altered the intrinsic activity of the particle-attached enzyme. Compared to KM, kcat appeared to be less sensitive to particle size and viscosity. © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng84: 406,414, 2003. [source] Close coupling approach in optically allowed atomic transitionsANNALEN DER PHYSIK, Issue 12 2007S. Bougouffa Abstract In general the calculations of the cross sections in atomic collisions theory need a treatment of a system of coupled integro-differential equations. We perform a numerical technique for calculations of electrons scattering with sodium atom. The cross sections are evaluated in the close coupling approach, where the problem is formulated in three coupling channel approximation. It is found that the three-channel problem results are typically in good agreement with experiment and two-channel calculations for intermediate energy range. The difference in the other range of energy can be assigned to the number of the used set of coupled differential equations in the 32S , 32P transition of sodium. [source] | ||||||||||