R.A. Gorse

Bio: R.A. Gorse is an academic researcher from University of California, Davis. The author has contributed to research in topics: Hydroxyl radical & Peroxide. The author has an hindex of 2, co-authored 2 publications receiving 86 citations.

A comprehensive modeling study of hydrogen oxidation

Abstract: A detailed kinetic mechanism has been developed to simulate the combustion of H2/O2 mixtures, over a wide range of temperatures, pressures, and equivalence ratios. Over the series of experiments numerically investigated, the temperature ranged from 298 to 2700 K, the pressure from 0.05 to 87 atm, and the equivalence ratios from 0.2 to 6. Ignition delay times, flame speeds, and species composition data provide for a stringent test of the chemical kinetic mechanism, all of which are simulated in the current study with varying success. A sensitivity analysis was carried out to determine which reactions were dominating the H2/O2 system at particular conditions of pressure, temperature, and fuel/oxygen/diluent ratios. Overall, good agreement was observed between the model and the wide range of experiments simulated. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 603–622, 2004

Rate Coefficients in the C/H/O System

Abstract: This chapter is a critical survey of reaction rate coefficient data important in describing high-temperature combustion of H2, CO, and small hydrocarbons up to C4. A recommended reaction mechanism and rate coefficient set is presented. The approximate temperature range for this mechanism is from 1200 to 2500 K, which therefore excludes detailed consideration of cool flames, low-temperature ignition, or reactions of organic peroxides or peroxy radicals. Low-temperature rate-coefficient data are presented, however, when they contribute to defining or understanding high-temperature rate coefficients. Because our current knowledge of reaction kinetics is incomplete, this mechanism is inadequate for very fuel-rich conditions (see Warnatz et al., 1982). For the most part, reactions are considered only when their rates may be important for modeling combustion processes. This criterion eliminates considering many reactions among minor species present at concentrations so low that reactions of these species cannot play an essential part in combustion processes. The philosophy in evaluating the rate-coefficient data was to be selective rather than exhaustive: Recent results obtained with experimental methods capable of measuring isolated elementary reaction rate parameters directly were preferred, while results obtained using computer simulations of complex reacting systems were considered only when sensitivity to a particular elementary reaction was demonstrated or when direct measurements are not available. Theoretical results were not considered.

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Abstract: . The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (~180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.

Stratospheric Ozone: An Introduction to Its Study

Abstract: An analysis is made of the various reactions in which ozone and atomic oxygen are involved in the stratosphere. At the present time, hydrogen, nitrogen, and chlorine compounds in the ranges parts per million, parts per billion, and parts per trillion may have significant chemical effects. In the upper stratosphere, above the ozone peak, where there is no strong departure from photochemical equilibrium conditions, the action of hydroxyl and hydroperoxyl radicals of nitrogen dioxide and chlorine monoxide on atomic oxygen and of atomic chlorine on ozone can be introduced. A precise determination of their exact effects requires knowledge of (1) the vertical distribution of the H2O, CH4, and H2 dissociation by reaction of these molecules with electronically excited oxygen atom O(¹D); (2) the ratio of the OH and HO2 concentrations and their absolute values, which depend on insufficiently known rate coefficients; (3) the various origins of nitric oxide production, with their vertical distributions related to latitude and season; and (4) the various sources giving different chlorine compounds that may be dissociated in the stratosphere. In the lower stratosphere, below the ozone peak, there is no important photochemical production of O3, but there exist various possibilities of transport. The predictability of the action of chemical reactions depends strongly on important interactions between OH and HO2 radicals with CO and NO, respectively, which affect the ratio n(OH)/n(HO2) at the tropopause level; between OH and NO2, which lead to the formation of nitric acid with its downward transport toward the troposphere; between NO and HO2, which lead to NO2 and its subsequent photodissociation; between ClO and NO, which also lead to NO2 and become more important than the reaction of ClO with O; and between Cl and various molecules, such as CH4 and H2, which lead to HCl with its downward transport toward the troposphere. All these chemical processes are subject to many changes since they occur in the lower stratosphere where seasonal, latitudinal, and even day-to-day variations of the ozone concentrations are observed in association with advective and dynamic transports, which depend on meteorological conditions as indicated by variations of tropopause heights.

The use of transition-state theory to extrapolate rate coefficients for reactions of H atoms with alkanes

Abstract: Conventional transition-state theory is used for extrapolating rate coefficients for reactions of O atoms with alkanes to temperatures above the range of experimental data. Expressions are developed for estimating structural properties of the activated complex necessary for calculating enthalpies and entropies of activation. Particular attention is given to the problem of the effect of the O atom adduct on the internal rotations in the activated complex. Differences between primary, secondary, and tertiary attack are discussed, and the validity of representing the activated complexes of all O + alkane reactions by a fixed set of vibrational frequencies and other internal modes is evaluated. Experimental data for reactions of O atoms with 15 different alkanes (CH4, C2H6, C3H8, C4H10, C5H12, C6H14, C7H16, C8H18, i–C4H10, (CH3)4C, (CH3)2CHCH(CH3)2, (CH3)3CC(CH3)3, c–C5H10, c–C6H12, c–C7H14) are reviewed. The following approximate expressions for ΔS‡(298) and E(298), the entropy and energy of activation, respectively, are consistent with the experimental data and with the calculations: where nC = number of carbon atoms in the alkane and nH = the number of “equivalent” H atoms. Using the conventional transition state theory expression, k(298) = 1015.06 exp(ΔS‡/R) exp(–E(298)/298R) L mol−1s−1, one then obtains: These expressions agree with experimental values within a factor approximately 2 for alkanes larger than C3H8.