Rate coefficient measurements for over fifty gas-phase bimolecular reactions were critically evaluated and compared to theoretical calculations. The results of this work are summarized here in forty-nine Data Sheets, one sheet for each reaction or set of reactions of a single pair of reagents. The reactions chosen are of interest in propulsion, combustion, and atmospheric chemistry. Each Data Sheet consists of two pages that include a brief resume of the important experimental measurements and theoretical calculations, a graphical presentation of the data, a recommended rate coefficient expressed as a function of temperature, k (T) = A Tnexp( -B IT), with probable uncertainty limits, a discussion of the basis for the recommendation, an equilibrium constant and a rate coefficient for the reverse reaction where applicable, and pertinent references.

A new program for the compilation and evaluation of chemical kinetic data is described. Rate coefficient measurements are assessed for probable accuracy and precision. Transition-state theory is often used to extrapolate measurements to higher temperatures. For every reaction reviewed, a recommended rate coefficient is given in the form k = ATn X exp( -B /T}. Pertinent data and conclusions are summarized on a two-page Data Sheet, each sheet covering one reaction or occasionally two or three closely related reactions. Twenty-seven Data Sheets are presented for reactions important in modeling and understanding chemical lasers, hydrogen-oxygen combustion, hydrocarbon oxidation, and aluminum or boron propellant systems.

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Conventional transition-state theory is used for extrapolating rate coefficients for reactions of 0 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 0 atom adduct on the internal rotations in the activated complex. Differences between primary, secondary, and tertiary attack are dis- are reviewed. The following approximate expressions for AS'(298) and E(298), the entropy and energy of activation, respectively, are consistent with the experimental data and with the calculations:

The photochemistry of trace amounts of isobutene and oxides of nitrogen in an atmosphere of air was studied both in the presence and in the absence of small amounts of carbon monoxide. Carbon monoxide accelerates the reaction as measured by nitric oxide oxidation or ozone formation. This finding has relevance to photochemical smog formation.