Engineering topics
Publications and source records attributed to Molina, L. T..
The production of Cl atoms in the laser flash photolysis of ClOOCl at 308 nm has been investigated by time-resolved atomic resonance fluorescence at 235 K. A value of phi = 1.03 +/-0.12 has been obtained for the primary quantum yield based on an absorption cross section ratio sigma(245)/phi(308) = 22 for ClOOCl at 245 and 308 nm.
A tunable diode laser spectrometer has been used to measure absorption coefficients of peroxynitric acid (HO2NO2) near the 803/cm Q branch. HO2NO2 concentrations in a low-pressure flowing gas mixture were determined from chemical titration procedures and UV absorption spectroscopy. The diode laser measured absorption coefficients, at a spectral resolution of better than 0.001/cm, are about 10 percent larger than previous Fourier transform infrared measurements made at a spectral resolution of 0.06/cm.
The species Cl2O2 has been generated in a gaseous flow system at 220-240 K by reacting Cl atoms with one of three different ClO precursors: O3, Cl2O, or OClO. The infrared spectra of the reactive mixture indicate that at least two different dimers are produced: a predominant form with bands centered at 1225 and 1057/cm attributed to ClOOCl, and a second form with a band at 650/cm attributed to ClOClO. The UV spectrum of the predominant form shows a maximum absorption cross section of about 6.5 x 10 to the -18th sq cm/molecule around 270 nm, with a wing extending beyond 300 nm. The implications of these results for the chemistry of the stratosphere are discussed.
The absorption cross sections of ozone have been measured in the wavelength range 185-350 nm and in the temperature range 225-298 K. The absolute ozone concentrations were established by measuring the pressure of pure gaseous samples in the 0.08to 300-torr range, and the UV spectra were recorded under conditions where less than 1 percent of the sample decomposed. The temperature dependence is significant for wavelengths longer than about 280 nm. The absorption cross-section values around 210 nm were found to be about 10 percent larger than the previously accepted values.
Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.
The reaction HCl + ClONO2 yields Cl2 + HNO3 has been studied by Fourier transform infrared spectroscopy and by a static wall-less UV absorption technique. An upper limit to the homogeneous bimolecular rate constant of 10 to the -19th cu cm/molecule per sec was established, making the reaction unimportant in the stratosphere.
The absorption spectra of three hydrazines and four of their air-oxidation products were measured in the 9-12-micron spectral region with a Fourier transform infrared (FTIR) spectrometer with a 0.05-kayser resolution to determine absorption coefficients at CO2 and tunable diode laser wavelengths. The measurements agreed well with published CO2 laser determinations for many of the absorption coefficients, except where the published values are thought to be in error. The coefficients were then used to estimate the sensitivity for remote detection of these gases using CO2 and tunable diode lasers in long-path differential absorption measurements.
Using the techniques of laser/flash photolysis-resonance fluorescence, the absolute rate constant for the OH + HCl reaction is measured from 240 to 295 K. Ultraviolet and infrared spectrophotometry are used to continuously monitor the HCl concentrations. It is shown that the rate constant values obtained in the study are 20-30 percent larger than those recommended by Smith and Zellner (1974) and Ravishankara et al. (1977) for modeling of stratospheric chemistry.
The ultraviolet absorption spectrum of carbonyl sulfide is investigated in order to assess the importance of the photolytic sink for OCS in the troposphere. Absorption cross sections were measured at wavelengths between 185 and 300 nm in a double-beam spectrometer at temperatures of 295 and 225 K. The results are found to be in good agreement with previous reports in the short wavelength region, but significantly lower than the value of 2 x 10 to the 22nd sq cm/molecule proposed by Rudolf and Inn (1981) between 280 and 300 nm, which may be attributed to trace contaminants or dimerization. A marked temperature effect is noted at wavelengths greater than 240 nm and below 190 nm. As no evidence of absorption at wavelengths greater than 270 nm was found, estimates of the solar photodissociation rate of tropospheric OCS based on the present cross sections yield a value of about 2 x 10 to the -9th/sec, corresponding to a tropospheric lifetime of about 20 years. It is therefore concluded that solar photolysis represents a negligible sink for OCS.
The ClO + NO2 + M reaction has been studied with two techniques: Fourier transform infrared spectroscopy of the products, and flash photolysis-ultraviolet absorption to monitor the decay of ClO in excess NO2. The measured third-order rate constant is 1.5 x 10 to the -31st cm to the 6th/molecule-squared per sec at 298 K with M = N2, in good agreement with previous literature values, but the rate constant appears to decrease by up to a factor of three in the presence of increasing amounts of OClO. For the infrared studies a stoichiometric mixture of ClO and NO2 was prepared in a flow system by mixing NO with OClO; at least as much NO2 as ClONO2 was produced under a variety of experimental conditions. These two sets of results are incompatible with the assumption made in previous kinetic studies that ClONO2 is the only recombination product; other isomers such as OClONO or ClOONO are likely to be formed three to four times faster. These results imply that potential stratospheric ozone depletion due to chlorofluoromethanes may be even larger than previously thought.
Laser-induced fluorescence has been used to measure the amount of OH produced in the laser photolysis of HOCl at 310 nm. The HOCl was generated by the Cl2O + H2O and by the HCl + Cl2O reactions. The laser technique samples OH on a microsecond time scale so that secondary radical reactions cannot contribute significantly to the observed signals. The fluorescence signals were calibrated with O3-H2O mixtures, the reactions O3 + h(nu) yields O(1D) + O2 and O(1D) + H2O yields 2OH yielding known amounts of OH. The value for the absorption cross section of HOCl at 310 nm has been determined to be 6 x 10 to the -20th sq cm, assuming K(eq) = 0.082 for the Cl2O + H2O yields 2HOCl system and assuming unit quantum yield for the production of OH. The present investigation further supports earlier experimental work concluding that HOCl will photodissociate rapidly and will not be an important holding tank for chlorine in the stratosphere. These results are in disagreement with theoretical calculations of the UV absorption spectrum of HOCl in the 300-350-nm wavelength region.
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The ultraviolet absorption cross sections of hydrogen peroxide vapor have been determined over the wavelength range 210 to 350 nm at 296 K. At the longer wavelengths, the gas phase absorptivities are significantly larger than the corresponding values in condensed phase. The atmospheric H2O2 photodissociation rate for overhead sun at the earth's surface is estimated to be about 1.3 x 10 to the -5th/sec.
The near-ultraviolet absorption spectrum of chlorine nitrite (ClONO) has been quantitatively investigated over the wavelength range 230-400 nm at 231 K. An absorption maximum was observed at 290 nm with a cross section of 1.5 by 10 to the -18th power sq cm. The calculated lifetime against photodissociation for ClONO in the atmosphere is 2 to 3 minutes. The large photolysis rate indicates that ClONO does not play a significant role in the stratosphere as a temporary holding tank for chlorine.
Experiments were conducted in a conventional fast flow apparatus to study the rate constant and the activation energy for the reaction O(3P) + ClONO2. The air-afterglow technique was used for the detection of oxygen atoms under pseudo first order conditions. A value of (3.4 plus or minus 0.6) x 10 to the -12th exp/(-840 plus or minus 60)T/cu cm/molecule/s was obtained for the rate constant. The observed rate is sufficiently slow so that oxygen atom attack is of minor importance in the stratosphere compared to photolysis.
High resolution infrared absorptivities of chlorine nitrate (ClONO2) are required in order to quantitatively evaluate, by examination of infrared spectra obtained recently from balloon-borne spectrometers, the possible occurrence of this compound in the stratosphere. In the present study, infrared absorptivities for four absorption bands of gaseous ClONO2 have been measured at 0.0625 per cm spectral resolution with a Fourier transform infrared (FT-IR) system. Spectra were obtained at two pressures (0.05 and 1.05 torr) of pure ClONO2 and with 125 torr of N2 added to a 0.50 torr sample. Absorptivities for a range of spectral resolutions (0.0625, 0.125, 0.25 and 0.50 per cm) have been calculated from the data.