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Measurements results are presented for the rate constant of the reaction OH + HCl yields H2O + Cl determined in a flow tube over the temperature range of 224 to 460 K using resonance fluorescence detection of OH. Stratospheric and reaction kinetic implications are briefly discussed.
An experimental, laboratory study of the various photochemical reactions that can occur in the mesosphere and stratosphere is presented. N2O was photolyzed at 2139 A in the presence of CH3OH and CO. The O(id) produced in the photolysis reacted with CH3OH to produce OH radicals, and thus the reactions of both O(id) and OH were able to be studied. Also considered was the oxidation of the HCO radical. Mixtures of Cl2, O2, H2CO, and sometimes N2 or He were irradiated at 3660 A at several temperatures to photodecompose the Cl2. The photochemical oxidation of formaldehyde was studied as follows: formaldehyde in the presence of N2 and/or O2 (usually dry air) was photolyzed with a medium pressure Hg lamp used in conjunction with various filters which transmit different relative amounts of Hg lines from 2894 A to 3660 A. Results are presented and discussed, along with a description of experimental procedures and apparatus, and chemical reaction kinetics.
The reaction OH + HN3 yields H2O + NO3 was studied over the temperature range 270-470 K in a flow system utilizing UV resonance fluorescence detection of OH. A temperature independent rate constant of (8.9 plus or minus 1.3) x 10 to the -14 cu cm/s was obtained, where the reported uncertainty represents a single standard deviation including estimates of systematic errors.
The intensity and pressure dependence of the fluorescence spectrum of OH in the presence of N2 and H2O molecules was studied. Saturation of the absorption transition was observed at low pressures, and the corresponding fluorescence signal was found to vary as the square root of the exciting intensity. This observed dependence agreed with the predicted dependence which took into account the presence of laser modes in the spectrum of the exciting radiation. With full laser power incident, a saturation parameter as high as 3 x 10 to the 5th was observed. The fluorescence spectrum was found to peak at 3145 and at 3090 A, with the relative peak intensities dependent upon gas pressures and upon the particular rotational electronic transition used for excitation. It is concluded that vibrational relaxation of the electronically excited OH due to water vapor in the system plays a dominant role in determining the observed fluorescence spectrum.
Photodissociation of OH dominates its destruction for a significant range of density and shielding in H I regions. Although inverse predissociation may provide an observable flux of ultraviolet recombination photons, it can provide only a small fraction of the total observed OH in most H I regions.
The OH airglow studies discussed have evolved from a lead-sulfide-cell scanning photometer to photographic techniques to, currently, image-tube photography. During the Space Shuttle Simulation, photography (35-mm and 16-mm) and filter-wheel photometry of submicron OH airglow were performed aboard the NASA CV990 Airborne Laboratory. Examples of ground-based and airborne photographs are presented for comparison. Analysis of the aircraft data is described.
Absorption of OH was measured using a CW tunable laser. Results indicate that this technique, when combined with frequency modulation, promises a sensitivity of 100,000 molecules/cu cm for OH monitoring in the atmosphere.
It is noted that recent measurements of large values of the rate coefficient for the reaction NO + HO2 yields NO2 + OH lead to model predictions of excessive amounts of stratospheric ozone. This letter shows that a recent measurement of the rate coefficient (k2) for the reaction HO2 + O3 yields OH + 2O2 largely resolves these problems of excessive stratospheric ozone in models. A two-dimensional model of stratospheric trace constituents is used to calculate the concentrations of 35 constituents; the results are compared with experimental measurements of ozone column densities. It is found that the model predictions of excess ozone abundances diminish significantly when the measured value of k2 is employed.
The mass, radius, and luminosity of 26 Mira variables that are known OH sources of radio emission at 1612 MHz have been estimated. The time-independent solution of Salpeter's (1974) stellar-wind equation and a period-density relation are used to solve for basic stellar parameters, with the aid of the terminal expansion velocity of the OH maser cloud. Masses obtained from these calculations are consistent with other estimated values for masses of Mira variables. Good agreement is obtained when comparing the rate of mass loss as determined from Reimers's (1977) semiempirical relation with estimates of the mass-loss rate as deduced from theoretical models involving radiation pressure on grains. These calculations suggest a strong correlation between the mass-loss rate and the pulsation period. Arguments concerning the general properties of silicate grains from radiation-pressure-driven stellar-wind equations are discussed.
Measurements indicate that ambient NOx(NO + NO2) concentrations vary over at least an order of magnitude in the troposphere. Thus it is of interest to study atmospheric chemistry with NOx concentrations covering this range. In this paper we present steady state calculations which show that as NOx concentrations are increased from very low values, the hydroxyl radical concentration increases at first and then decreases. This change of behavior occurs at a concentration of NO2 of about 0.23 ppb in the model. Also, the response of the atmosphere to increased CO fluxes undergoes a qualitative change as a function of the concentration of NOx. At low levels of NOx concentration, an increase in CO fluxes into the atmosphere depletes the OH concentration and increases the concentrations of CH4 and H2, as reported in the literature. However, at high values of NOx concentration, increased CO fluxes give rise to an increase in the OH concentration and, consequently, a decrease in the concentrations of CH4 and H2.
Recent concern about the depletion of stratospheric ozone by chlorine species from the decomposition of chlorofluoromethanes has emphasized the need for laboratory studies of the first reaction steps involved, especially those which control the concentration of the OH and ClO radicals in the stratosphere. Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K have been determined in a discharge flow system using resonance fluoresence detection. The results are (9.1 + or - 1.3) x 10 to the -12th, (5.5 + or - 0.3) x 10 to the -14th, and (6.5 + or - 0.5) x 10 to the -12th (all in units of cu cm/sec), respectively.
A 163 micron (1.836 THz) radiometer developed for airplane and/or balloon platforms is described. The laser local oscillator is a CO2 pumped methanol laser operating at a frequency which is approx. 1 GHz from the J = 3/2 - 1/2 transition of OH. The laser is used directly as a local oscillator or is translated in frequency to closer coincidence with the OH emission, depending on achieved detector IF bandwidth. Frequency translation techniques which are described are diode mixing and a method of single sideband generation using an external Stark modulated gas cell. The photoconductive mixer used is a strained Ge crystal, doped with Ga, originally used as an incoherent detector. The uniaxial strain on the Ga doped Ge crystal shifts the threshold for photoconduction from 100/cm to frequencies as low as 50/cm. These detectors are currently being characterized as mixers in the laboratory. Of particular interest are the effect of local oscillator power and strain on IF, bandwidth detector impedance, and conversion loss. Preliminary results of these tests are described and compared with theorectical expectations.
The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.
Direct lifetime measurements at pressures up to 25 torr are used to determine the quenching rates for the A 2 Sigma + (v = 0) state of OH due to N2, O2, H2O, and air. The results are found to corroborate quenching values obtained in a similar manner in the millitorr pressure range and show that the quenching cross sections of N2 is pressure independent at least up to 25 torr, that the quenching cross section of O2 is also likely to be pressure independent, and that the quenching values deduced from low-pressure experiments can be safely employed for atmospheric measurements of OH.
The homogeneously broadened linewidth of OH due to collisions with water molecules was found to decrease with increasing rotational excitation, and tended to level off to a constant value. This observed dependence is a manifestation of the rotational distribution of the water molecule through rotational transitions in near resonance with those of the OH. The constant value at high rotational excitation reflects the nonresonant contributions to the homogeneous linewidth similar to those due to nonpolar molecules.
The paper describes an experimental study of the title reaction that uses the discharge-flow technique, laser-induced-fluorescence detection of OH and simultaneous monitoring of O and H atoms in the 250-459 K range. The reaction is normal and free from surface effect interference in Teflon or halocarbon wax-coated tube, but not in clean Pyrex. OH radicals are generated in three ways and at low concentrations to eliminate side reactions. The rate constants were determined at 298 K and over the 250-459 K range, with a factor of two higher at 298 K and factors of 3 to 5 higher at 10 to 30 km altitude in the terrestrial atmosphere than previous studies have indicated. The effect of the higher rate constant on atmospheric processes and on recent laboratory measurements of other reactions is also discussed.
Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.
There is growing observational evidence that stratospheric OH concentrations are smaller than models have been predicting. Using very recent HOx reaction rate coefficient measurements in a two-dimensional photochemical model, results which support these observations are obtained. As a consequence of smaller OH concentrations, we show that perturbations of stratospheric ozone by NOx (SST emissions and nitrogen fertilizers) may be larger than expected, while perturbations due to added water vapor and chlorine (SSTs and chlorofluoromethanes, respectively) may be smaller.