Engineering topics

Cantrell, C. A.

Publications and source records attributed to Cantrell, C. A..

7 records

NASA NTRS2009

Inferring Ozone Production in an Urban Atmosphere using Measurements of Peroxynitric Acid

Observations of peroxynitric acid (HO2NO2) obtained simultaneously with those of NO and NO2 provide a sensitive measure of the ozone photochemical production rate. We illustrate this technique for constraining the ozone production rate with observations obtained from the NCAR C-130 aircraft platform during the Megacity Initiative: Local and Global Research Observations (MILAGRO) intensive in Mexico during the spring of 2006. Sensitive and selective measurements of HO2NO2 were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO2NO2 concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO2NO2 is 1.18. At NOx levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO2NO2 of 1.57. As a result, we find that at high NOx, the ozone production rate calculated using measured HO2NO2 is faster than predicted using accepted photochemistry. Inclusion of an additional HOx source from the reaction of excited state NO2 with H2O or reduction in the rate constant of the reaction of OH with NO2 improves the agreement.

Spencer, K. M.↗

NASA NTRS1991

An upper limit for the rate coefficient of the reaction of NH2 radicals with O2 using FTIR product analysis

Fourier transform infrared spectrometry has been used to study the products of the photooxidation of ammonia in the presence of oxygen at 296 K. The data have been used to derive an upper limit of 6 x 10 exp -21/cu cm molecule s for the reaction of NH2 radicals with O2 to produce NO(x) at 296 K. This upper limit, which is three orders of magnitude lower than previous estimates based on the kinetics of NH2 loss, rules out the importance of this reaction in the atmosphere and suggests that NH2 will be oxidized by O3 or NO2. The effect on the NO(x) and N2O budgets depends critically on the products of the NH2 + O3 reaction. Simulations of the experimental product yields also allow an evaluation of possible product channels for the reaction of NH2 with HO2.

Tyndall, G. S.↗

NASA NTRS1988

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.↗

NASA NTRS1988

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.↗

NASA NTRS1987

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.↗

NASA NTRS1987

Temperature variable long path cell for absorption measurements

The design and construction of a long path cell for absorption measurements at temperatures ranging from 215-470 K and at pressures from vacuum to 10 atm are described. The cell consists of three concentric stainless-steel tubes; the innermost tube is 6.5-in. in internal diameter, has a volume of about 47 l, and contains White-type optics, six thermocouples, and a gas input tube; and the outermost tube provides a vacuum Dewar around the inner assembly. The optical design and temperature control system for the long path temperature variable cell are examined. The long path cell is applicable for analyzing temperature and pressure dependence of spectra and reaction rates of gases, and the cell has flow and photolysis capabilities for studying transient species and photochemically initiated reactions. A diagram of the cell is provided.

Shetter, R. E.↗

NASA NTRS1987

Carbon kinetic isotope effect in the reaction of CH4 with HO

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Davidson, J. A.↗