Solar photolysis of water
Photolysis and regeneration reactions could be used in cycle process to generate hydrogen gas from water using sunlight.
Ryason, P. R.↗
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CO2 photolysis revisited
Measurements have been made of the absolute oxygen atom yields from CO2 photolysis at 1470 and 1302-1306 A; in both cases the yield is unity. The CO generation rates have also been measured in these two wavelength regions, and they are proportional to the oxygen atom generation rates; by implication the CO quantum yields are thus also unity. The CO deficiencies observed in earlier work on this subject are probably caused by heterogenous processes.
Slanger, T. G.↗
A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3
The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.
Kurylo, M. J.↗
Tropospheric UV flux calculations and photolysis rates for use with zonally and diurnally averaged models
A computationally fast and efficient method for calculating solar UV fluxes in the troposphere is developed. Calculated fluxes compare favorably with more rigorous multiple scattering results, and qualitatively correct behavior of the direct and diffuse flux components is maintained. In view of the relatively large uncertainties in other aspects of tropospheric photochemical models, the use of approximate UV flux calculations appears warranted. The technique is applied to the calculation of photolysis rates for twelve significant photolytic reactions of nine species.
Matloff, G. L.↗
A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl
The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.
Ravishankara, A. R.↗
Stratospheric ozone decrease due to chlorofluoromethane photolysis - Predictions of latitude dependence
A two-dimensional model is used to predict the 1990 reduction in ozone due to the chlorine compounds formed by chlorofluoromethane (CFM) photolysis when the CFM release rate is held constant at the 1975 value. The predicted globally averaged ozone reduction of 3.5% is similar to that predicted by one-dimensional models that did not include chlorine nitrate chemistry, and used lower values for the reactions rates of NO + HO2 yielding NO2 + OH and O3 + HO2 yielding OH + 2O2. When the 5.7 ppbv increase in chlorine compounds predicted by one-dimensional models to occur under steady-state conditions is simulated by the two-dimensional model, a 26% decrease in atmospheric ozone is predicted. The latitude dependence of the ozone reduction is discussed in terms of the relevant photochemical reaction and transport. The chemical reactions that most strongly influence the meridional dependence of the ozone depletion are identified as those associated with the reactions of chlorine monoxide and atomic oxygen, the recombination of ozone and atomic oxygen, and the photodissociation of molecular oxygen.
Borucki, W. J.↗
Production of OH from photolysis of HOCl at 307-309 nm
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.
Molina, M. J.↗
Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm
The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.
Brock, J. C.↗
Ozone photolysis - Determination of the O/3P/ quantum yield at 266 nm
Direct production of O(3P) from the photodissociation of O3 at 266 nm has been observed by time-resolved resonance fluorescence following laser flash photolysis. The quantum yield for O(3P) production was determined to be 0.12 + or - 0.02 at this wavelength. This result confirms the qualitative observations of two previous photofragment studies and establishes an absolute value of the quantum yield for O(1D) production of 0.88. This value has been used as a basis for normalizing relative quantum yields in the fall-off region, and interpreting O(1D) kinetics studies.
Brock, J. C.↗
A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence
The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.
Bosco, S. R.↗
A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O
Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.
Wine, P. H.↗
Pulsed laser photolysis study of the reaction between O(3P) and HO2
It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.
Ravishankara, A. R.↗
Partitioning of excess energy in the photolysis of cyanogen chloride and cyanogen bromide at 193 nm
The nascent quantum state distributions of CN(X2 Sigma +) fragments produced in the dissociation of ClCN and BrCN by photolysis at 193 nm, in an effusive beam, have been measured. The rotational distribution of the fragments is highly excited. The results show that the excited electronic state which dissociates is bent. A simple parameterization is shown to fit the results. This parameterization is based on a semiclassical model which has dynamical implications.
Halpern, J. B.↗
Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains
With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.
Ferris, J. P.↗
Photochemical reactions in interstellar grains photolysis of CO, NH3, and H2O
The interstellar grains are currently considered to be the basic building blocks of comets and, possibly, meteorites. To test this theory, a simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH3:H2O gas mixture on an Al block at 10 K, with concomitant irradiation with vacuum UV. The results of the HPLC and IR analyses of the nonvolatile residue formed by photolysis at 10 K are compared with those observed at 77 K and 298 K. Some of the compounds that may be present on the surfaces of interstellar dust particles have been identified, and some specific predictions concerning the types of molecular species present in comets could be drawn. The results also suggest that photochemical reactions may have been important for the formation of meteorite components. The implication of the findings to the questions of the source of organic matter on earth and the origin of life are discussed.
Agarwal, V. K.↗
Production of isotopically heavy ozone by ultraviolet light photolysis of O2
Ozone was produced by UV photolysis (157-200 nm) of molecular oxygen. The product ozone is enriched in O-17 and O-18 on a mass-independent basis, similar to the fractionations observed in an electrical discharge. The magnitude of O-18 and O-17 enrichment decreases with decreasing pressure, suggesting the presence of two fractionation mechanisms with differing delta-O-17/delta-O-18 ratios. One of the end members would be mass-independent with delta-O-18 equal to delta-O-17 equal to about 90 percent, which is dominant above about 20 torr. The second process which is significant below about 6 torr produces O3 with delta-O-18 equals about -55 percent, delta-O-17 equals about -27.5, possibly due to isotopic selectivity in diffusion to the reaction systems wall. The delta-O-17 = delta-O-18 isotopic fractionation resembles that observed in stratospheric ozone, though the magnitude of fractionation is a factor of four less.
Thiemens, Mark H.↗
Temperature dependence of the atmospheric photolysis rate coefficient for NO2
Accurate values for the photolysis rate coefficient of NO2 (j1) are required for studies related to the observed imbalance in the photostationary state of O3, NO, and NO2 in the troposphere. Direct measurements of the temperature dependence of j1 at temperatures from -70 to 30 C were made in sunlight for relatively cloudless summer days in Boulder, Colorado. The ratios of j1 (30 C)/j1 (T C) for T = -10 C and -70 C, respectively, were 1.046 + or - 0.040 and 1.070 + or - 0.031. The j1 ratios were independent of solar zenith angle. Theoretical estimates of the temperature-dependent j1 ratios based upon recently reported cross section (sigma) and quantum yield (phi) data are more consistent with these experimental measurements than those based upon the currently accepted sigma and phi data.
Shetter, Richard E.↗
Pulsed laser photolysis kinetics study of the O(3P) + ClO reaction
A pulsed laser photolysis technique was used to investigate the kinetics of the important stratospheric reaction O + ClO yields Cl + O2 in buffer gas over the temperature and pressure ranges of 231-367 K and 25-500 torr. The results indicate a lack of pressure dependence at 298 K over the 25-500 torr range.
Nicovich, J. M.↗