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Mcdaniel, A. H.

Publications and source records attributed to Mcdaniel, A. H..

Visible-ultraviolet absorption cross sections for NO2 as a function of temperature

A redetermination of the temperature dependence of the absorption cross-section (sigma) of NO2 in the visible-ultraviolet region was made in order to provide a more reliable data base for the calculation of NO2 photolysis rates in the atmosphere. Experiments over a wide range of temperatures and NO2 concentrations were conducted. The integral of a plot of sigma versus the inverse of the wavelength was essentially independent of temperature. Increasing temperature produced a shift of the spectrum toward longer wavelengths, resulting in a small negative temperature dependence of sigma over the 264-400 nm range and a small positive dependence over the 450-649 nm range. Increasing temperature produced broadening of individual spectral features, resulting in a systematic lowering of peaks and filling of valleys. Recommended cross sections are presented for use in tropospheric NO2 photolysis rate calculations.

Davidson, J. A.↗

The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

Cantrell, C. A.↗

Atmospheric infrared emission of ClONO2 observed by a balloon-borne Fourier spectrometer

ClONO2 was observed in high-resolution infrared emission spectra obtained on Nov. 6, 1984, by a balloon-borne Fourier spectrometer. The observations took place near 0300 LT at a latitude of 35 N. Spectral simulations are used to determine the mixing ratios of ClONO2. This analysis incorporates line by line calculations and new ClONO2 cross sections measured in the laboratory at 223 K. The inferred mixing ratios of ClONO2 are 1.3 + or - 0.45 ppb and 0.98 + or - 0.35 ppb at 14 and 34 mbar. One-dimensional photochemical model predictions are compared to the observations. The ClONO2 mixing ratio at 34 mbar appears to be larger than theory, while there is agreement at 14 mbar.

Massie, S. T.↗