Engineering topics
Publications and source records attributed to Sander, S. P..
A calculation of the A(sup 2)(Sigma) leads to...X(sup 2)II (0,0) band emission rate factors and line center absorption cross sections of OH applicable to its measurement using solar resonant flourenscence in the terrestrial atmosphere is presented in this paper.
The presence of fluorine containing compounds (e.g. HF and COF2) in the Earth's atmosphere is thought to be due solely to the decomposition of man-made chemicals such as chlorofluorocarbons and hydrofluorocarbons. The effect on atmosphere ozone of reactive fluorine-containing intermediates produced during CFC and HFC decomposition has attracted significant interest recently.
This is the eleventh in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.
Concentrations of HCl measurements in the lower stratosphere in 1993 by the ALIAS instrument on the ER-2 aircraft reveal that only 40% of inorganic chlorine (Cl(y), inferred from in situ measurements of organic chlorinated sources gases) is present as HCl, significantly lower than model predictions. Although the sum of measured HCl, ClO and ClONO2, the latter inferred from measurements of ClO and NO2 equals Cl(y) to within the incertainty of measurement, it is systematically less than Cl(y) by 30-50%. This discrepancy suggests that concentrations of ClONO2 may exceed those of HC; near 20 km altitude, consistent with a slower photolysis rate for ClONO2 than calculated using recommended cross sections. Comparison of profiles of HCl measured during 1992 and 1193 at mid-latitudes by balloon (BLISS and MARKIV), space shuttle (ATMOS), and satellite (HALOE) instruments with the aircraft data reveal an apparent pressure dependence to the HCl to Cl(y) ratio, consistent with a factor of 3-10 reduction in the photolysis rate for ClONO2 at ER-2 altitudes. However, the diurnal variation of ClO is well-simulated by models using the recommended photolysis rate, and simulations measurements of ClONO2 and HCl at mid-latitudes by ATMOS and MARKIV report HCl (HCL+ ClONO2) ratios greater than or equal to 50%. Premliminary measurements by ALIAS in the southern hemisphere report HCl/Cl(y) values of about 75%.
The atmospheric lifetimes of molecules containing chlorine and bromine are the dominant parameters influencing their ability to promote enhanced ozone destruction in the stratosphere. The purpose of this report is to assess the present state of knowledge of the lifetimes of halocarbons using two complementary approaches. First, a time series of measurements of gas concentrations is used together with information on their emissions histories and a computational model of atmospheric circulation and chemistry to infer lifetimes through a mass balance approach. Second, an atmospheric chemical-dynamical model is used with detailed information on the chemistry and spectroscopy of the molecules of interest to calculate lifetimes. The lifetimes determined by these two methods are then compared. Attention is focused most closely on fully halogenated chlorine- and bromine-containing molecules, primarily the chlorofluorocarbons, and the halons, because of their ability to deliver chlorine and bromine to the stratosphere. Some attention will be given to those molecules containing hydrogen, which are subject to removal in the troposphere primarily by reaction with OH and by other processes.
Production of electronic ground state NO(sub 2) from 248 nm photolysis of HNO(sub 3) was detected by laser induced fluorescence (LIF). A growth in the LIF signal was observed following the photolysis and has been interpreted as the relaxation of NO(sub 2) through the higher vibrational levels of the X state; an energy region where the probe laser photodissociates the NO(sub 2) instead of inducing fluorescence.
The structure of ClO2 has been calculated for the X 2A-double prime ground state using unrestricted Hartree-Fock (UHF), unrestricted second-order Moller-Plesset perturbation (UMP2), configuration interaction employing single and double excitation (CISD), and quadratic configuration interaction (QCI) ab initio molecular orbital methods. Calculations using UMP2 and CISD wave functions predict a ClO bond length of 1.728 +/- 0.01 A. The single-configuration-based QCI in the singles and doubles space with perturbation inclusion of triple substitutions, denoted QCISD(T), yield a ClO bond length of 2.205 A. The QCI results are consistent with results of Jensen (1990) who showed that the ClO bond length is 2.181 A using annihilated self-consistent methods (AUMP2). The thermochemistry of ClO2 radical has been calculated using MP2 and QCI methods employing an isodesmic scheme. Our scheme predicts the heat of formation for ClO2 at 0 K to be 24.6 +/- 2 kcal/mol.
As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory.
The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.
Second-order rate constants for the decay of O(3P) in excess chlorine dioxide, k(II), were measured as a function of total pressure (20-600 Torr argon) and temperature (248-312 K), using flash photolysis-atomic resonance fluorescence. Results indicate that k(II) is pressure dependent with a value, K(b), that is nonzero at zero pressure, and both the third-order rate constant and k(b) have negative temperature dependences.
Some vibronic transitions of ClO such as G(v-prime = 11 )-X(v-double prime = 10), G(v-prime = 5)-X(v-double prime = 3) and H(v-prime = 4)-X(v-double prime = 2), which promote overtones of X(2pi3/2) to bound Rydberg states, are nearly resonant with the 130.6 nm O-atom emission line and possess sizable Franck-Condon factors. On this basis broadband detection of 'O atom' fluorescence in experiments involving vibrationally excited ClO(X) is ascribed to the radiative decay of ClO(G, H) rather than to the formation of O atoms; these observations raise the probability of monitoring ClO(X; v = 0) by VUV-induced fluorescence.
Integrated band intensities of the 620/cm absorption in (C2H2)2 are measured by FTIR spectroscopy at constant acetylene pressure between 198 and 273 K. These data, in conjunction with ab initio results for (C2H2)2, are used for the statistical evaluation of the equilibrium constant Kp(T) for acetylene-cluster dimerization. The present results are used to clarify the role of molecular clusters in chemical systems at or near equilibrium, in particular in Titan's stratosphere.
The kinetics of ozone destruction within the Antarctic polar vortex are studied via simultaneous in situ observations of ClO, BrO, O3, N2O, pressure, and temperature. It is found that the chlorine dimer mechanism rate, limited by the reaction ClO + ClO + M yields ClOOCl + M, contributes the most to the integrated rate of ozone destruction within the vortex on isentropic surfaces between altitudes of 14 and 18.3 km.
This is the eighth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109.
The flash photolysis-visible absorption technique has been used to measure rate constants for the reaction NO + NO3 2NO2 over the temperature range 224-328 K. The temperature dependence of the rate constant is given by the expression K1(T) = (1.59 + or - 0.32) x 10 to the -11th exp(122/T)cu cm/molecule/s where the stated uncertainties refer to the + or - sigma limits from both random and systematic errors.
The flash photolysis-absorption technique has been used to measure the rate constant for the reaction IO + IO over the temperature range 250-373 K and pressure range 20-700 torr of N2. The rate constant for the overall reaction was found to be independent of pressure and equal to 1.73 x 10 to the -12th exp (1020 + or - 200)/T cu cm/molecule s. Branching ratios for the reaction channels forming 2I + O2, I2 + O2, and I2O2, were found to be pressure dependent, with the I2 channel accounting for less than 5 percent of the total reaction over the observed pressure range. A stable reaction product was observed between 230 and 300 nm which was formed on a long time scale compared to IO disappearance. The rate constant for the reaction I + O3 + yields to IO + O2 was measured at 298 K and found to be (9.5 + or - 1.5) x 10 to the -13th cu cm/molecule s.
Recent improvements in the data base for the currently identified reactions describing the chemistry of the major families of trace gas species, HO(x), NO(x), ClO(x), and hydrocarbons are assessed. The important coupling reactions between the families are introduced progressively. Chemical aspects such as heterogeneous reactions and reactions of sodium species, the importance of which are not yet completely established, are discussed. Recent attempts to reconcile some of the more unexpected kinetic behavior which has emerged from the extensive experimental studies of key reactions with current reaction rate theory are also examined. The uncertainties in the current kinetic and photochemical data base is given. The prospects for improvement of data for known reactions of atmospheric importance as well as for the identification of gaps in the chemical description of the atmosphere.
The flash photolysis/ultraviolet absorption technique was used to measure the rate constants for the reaction HO2 + NO2 + M yields HO2NO2 + M over the pressure range 50-700 torr and temperature range 229-362 K using He, O2, and N2 as diluent gases. The data were fit to the expression derived by Troe (1979) and co-workers for describing the pressure and temperature dependence of reactions in the falloff region. By combining these data with recent measurements of the rate constant for HO2NO2 thermal decomposition values of 73.8 + or - 2 eu for the standard entropy and -12.6 + or - kcal/mol for the standard enthalpy of formation of HO2NO2 were obtained. A significant enhancement in the rate constant was observed when water vapor was added to the system.