The present status of stratospheric science is discussed. The three basic elements of stratospheric science-laboratory measurements, atmospheric observations, and theoretical studies are presented along with an attempt to predict, with reasonable confidence, the effect on ozone of particular anthropogenic sources of pollution.

The stratosphere: Present and future

We present direct ab initio dynamics studies of thermal and vibrational‐state selected rates of the hydrogen abstraction CH4 +Cl↔CH3+HCl reaction. Rate constants were calculated within the canonical variational transition state theory formalism augmented by multidimensional semiclassical tunneling corrections. A vibrational diabatic model was used for vibrational‐state selected rate calculations, particularly for exciting the CH4 symmetric stretching and umbrella bending modes. The potential energy information was calculated by a combined density functional and molecular orbital approach. Becke’s half‐and‐half (BH&H) nonlocal exchange and Lee–Yang–Parr (LYP) nonlocal correlation functionals (BH&HLYP) were used with the 6‐311G(d,p) basis set for determining structures and frequencies at the stationary points and along the minimum energy path (MEP). Energetics information was further improved by a series of single point spin‐projected fourth‐order Mo/ller–Plesset perturbation theory (PMP4(SDTQ)) calculation...

Thermal and vibrational‐state selected rates of the CH4+Cl↔HCl+CH3 reaction

A new potential energy surface is reported for the gas-phase reaction Cl+CH4→HCl+CH3. It is based on the analytical function of Jordan and Gilbert for the analog reaction H+CH4→H2+CH3, and it is calibrated by using the experimental thermal rate coefficients and kinetic isotope effects. The forward and reverse thermal rate coefficients were calculated using variational transition state theory with semiclassical transmission coefficients over a wide temperature range, 200–2500 K. This surface is also used to analyze dynamical features, such as reaction-path curvature, the coupling between the reaction coordinate and vibrational modes, and the effect of vibrational excitation on the rate coefficients. We find that excitation of C–H stretching modes and Cl–H stretching modes enhances the rate of both the forward and the reverse reactions, and excitation of the lowest frequency bending mode in the CH4 reactant also enhances the rate coefficient for the forward reaction. However, the vibrational excitation of t...

Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH4→HCl+CH3

Absolute rate coefficients for the reactions of chlorine atom with methane and ethane between 292 and 800 K and with propane between 292 and 700 K have been determined using the laser photolysis/co...

Kinetics of Cl Atom Reactions with Methane, Ethane, and Propane from 292 to 800 K

Rate constants for the reaction of N(4S) with NO have been measured from 196–400 K with two independent techniques both which utilize resonance fluoresence detection for temporal analysis of N(4S). The reaction has been studied at 196, 297, and 370 K by the discharge flow‐resonance fluorescence technique (DF‐RF) and the measured rate constant is best represented by the temperature independent value of (2.7±0.4) ×10−11 cm3 molecule−1 s−1. The technique of flash photolysis‐resonance fluorescence (FP‐RF) has been used to study the reaction at 233, 298, and 400 K, and the results are best represented by the temperature independent value of (4.0±0.2) ×10−11 cm3 molecule−1 s−1. Combination of the results suggests a value of (3.4±0.9) ×10−11 cm3 molecule−1 s−1 between 196–400 K. In this work discrimination between O(3P) atom and N(4S) atom fluorescence was necessary, and this was accomplished by inclusion of an O atom resonance line filtering section as an integral part of the resonance lamp. The suggested value for the rate constant is combined with a statistical mechanical evaluation of the equilibrium constant for N(4S)+NO=N2+O(3P) to give a revised estimate for the rate constant of the back reaction. The back reaction is important in the Zeldovich mechanism for thermal production of NO in combustion systems. The rate constant is also theoretically discussed in terms of collision theory.

Absolute rate of the reaction of N(4S) with NO from 196–400 K with DF–RF and FP–RF techniques

Rate constants for the reaction of atomic chlorine with methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

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Absolute rate of the reaction of Cl(2P) with methane from 200–500 K

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

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D. A. Whytock

Papers

Absolute rate of the reaction of Cl(2P) with methane from 200–500 K

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265–400 K