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At least 181 records · Page 10

Photolysis of vic-triazoles.

Photolytic cleavage of vic-triazole ring when unsubstituted at N, finding phenylacetonitrile production mechanism

Boyer, J. H.↗

Photolysis of formaldehyde at 1470 and 1236 A

Formaldehyde vapor photodecomposition modes by end product analysis, utilizing mixed isotope, radical scavenger, inert gas pressurization and lamp intensity attenuation

Glicker, S.↗

Laboratory CO2 photolysis studies related to planetary atmospheres

The CO(a 3II) state, the upper state of the Cameron bands, was characterized with respect to its average radiative lifetime and its quenching coefficients for a series of simple molecules. The CO2 recombination reaction (O(3P) + CO + M yields CO2 + M) was studied as a function of temperature. For M = CO, the rate constant can be expressed as k = 6.5 x 10/33 exp(-4340 plus or minus 550/RT) cm to the 6th power molec/2 sec/1, whereas the rate for M = CO2, the pertinent species in the planetary atmospheres, is 1.6 times greater. The quantum yield for CO2 photodissociation was measured in the 1200-1500 A region, using atomic line sources. The yield throughout this spectral region was much lower than that measured at 1470 A, the lowest value obtained being 8% at 1304 A.

Slanger, T. G.↗

The photolysis of ozone

Ozone was photolyzed at 25 C with steady illumination at several wavelengths from 2288 to 2850 A, at O3 pressures from 0.1 to 2.7 torr, and at absorbed intensities from 0.15 to 65 microns/min. Experiments were done in pure dry O3, and in the presence of He, CO2, N2, H2O, H2, N2O, He-CO2, He-H2O, CO2-H2O, O2-N2O, CO2-O2, and N2O5-O2-CO2 mixtures. The results show that in the absence of added gases or in the presence of He, the quantum yield of O3 consumption is 5.5 independent of conditions, except at pressures below 0.4 torr. In the presence of CO2 or N2, ozone consumption falls toward 4.0. The primary photolytic act produces O(1 D) and siglet O2, presumably O2(1 delta), at all wavelengths below 3000 A. Relative quenching constants O(1 D) removal by various gases were measured at 2288, 2537, and 2800 A. For O3, CO2, and N2, the relative rates are 1.0/0.4 to 0.5/0.08 to 0.11 at all wavelengths. For H2O the constant at 2537 A is 1.5 relative to that for O3. With N2O, a noticeable wavelength effect is observed and the relative rate constants are 1.5, 2 to 3, 4.0 for O3 compared to N2O at 2800, 2537, and 2288 A, respectively.

Lissi, E.↗

Dual photon effects in nitrogen dioxide photolysis

A previous study demonstrated two-photon consecutive absorption as being the most probable mechanism for the photodissociation of NO2 using a pulsed ruby laser at 6943 A. Additional data discussed here confirmed this and also examined an associated phenomenon, that of multiphoton induced fluorescence. The dissociation of NO2 by ON-O bond cleavage requires 3.4 eV, while the laser energy corresponds to 1.785 eV. The pooling of the energy of two photons would give more than enough energy to dissociate the NO2 into NO + O. Several mechanisms including (1) simultaneous absorption of two photons; (2) reaction of two singly excited NO2; (3) reaction of a singly excited NO2 with a ground state NO2; and (4) consecutive absorption of two photons were examined.

Hakala, D.↗

Vacuum UV photolysis of N2O

Emission from N2 B (3 Pi g) and O(1 S) produced during vacuum UV irradiation of N2O was studied as a function of the wavelength of the incident radiation. Two different processes were responsible for producing N2(B 3 Pi g) close to its production threshold. One process formed B 3 Pi g molecules directly and one indirectly via an unidentified precursor having a lifetime about 27 microsec. The quantum yield of O(1 S) atoms produced by photodissociation of N2O was determined as a function of incident photon energy. This yield is near 100% at 129 nm.

Mcewan, M. J.↗

Exponential approximation for daily average solar heating or photolysis

When incorporating formulations of instantaneous solar heating or photolytic rates as functions of altitude and sun angle into long range forecasting models, it may be desirable to replace the time integrals by daily average rates that are simple functions of latitude and season. This replacement is accomplished by approximating the integral over the solar day by a pure exponential. This gives a daily average rate as a multiplication factor times the instantaneous rate evaluated at an appropriate sun angle. The accuracy of the exponential approximation is investigated by a sample calculation using an instantaneous ozone heating formulation available in the literature.

Cogley, A. C.↗

Hydrogen from the solar photolysis of water

Developments related to the study of photosynthesis are examined and aspects of photosensitization by solids are considered. It is pointed out that solids photosensitization for solar photochemical fuel formation is now an extremely active research area as a consequence of the promising results obtained with semiconductor photoelectrodes. The investigation of water decomposition schemes involving heterogeneous reactions is likely to be a productive area. As is the case for photosynthesis, the known examples of water decomposition by solids photosensitization involve charge separation processes immediately following light absorption. Homogeneous photoredox reactions are also discussed, taking into account thermochemical and photochemical cycles leading to the formation of a photooxidized ion, hydrogen quantum yields in the photo-oxidation aqueous ions, and thermochemical and photochemical cycles leading to the formation of a photoreduced ion.

Ryason, P. R.↗

The photolysis of chlorine in the presence of ozone, nitric acid and nitrogen dioxide

The following three systems were investigated: the Cl2-O3 system, the Cl2-O2-NO system and the Cl2-NO2-M system. In the first system, the reaction between ClO and O3, the reaction between OClO and O3, and the mechanism of the Cl2-O3 system were studied. In the second system, the reaction between ClOO and NO was investigated. In the last system, the reaction between Cl and NO2 was investigated as well as the kinetics of the chemiluminescence of the Cl-NO2-O3 reaction. In the first system, Cl2 was photolyzed at 366 nm in the presence of O3 within the temperature range 254-297 K. O3 was removed with quantum yields of 5.8 + or - 0.5, 4.0 + or - 0.3, 2.9 + or - 0.3 and 1.9 + or - 0.2 at 297, 283, 273, and 252 K respectively, invariant to changes in the initial O3 or Cl2 concentration, the extent of conversion or the absorbed intensity, I sub a. The addition of nitrogen had no effect on -phi(03). The Cl2 removal quantum yields were 0.11 + or - 0.02 at 297 K for Cl2 conversions of about 30%, much higher than expected from mass balance considerations based on the initial quantum yield of 0.089 + or - 0.013 for OClO formation at 297 K. The final chlorine-containing product was Cl2O7. It was produced at least in part through the formation of OClO as an intermediate which was also observed with an initial quantum yield of phi sub i(OClO) = 2500 exp(-(3025 + or - 625)/T) independent of (O3) or I sub a.

Stuper, W. W.↗

Ammonia photolysis and the greenhouse effect in the primordial atmosphere of the earth

Photochemical calculations indicate that in the prebiotic atmosphere of earth ammonia would have been irreversibly converted to N2 in less than 40 years if the ammonia surface mixing ratio were no more than 0.0001. However, if a continuous outgassing of ammonia were maintained, radiative-equilibrium calculations indicate that a surface mixing ratio of ammonia of 0.0001 or greater would provide a sufficient greenhouse effect to keep the surface temperature above freezing. With a 0.0001 mixing ratio of ammonia, 60% to 70% of the present-day solar luminosity would be adequate to maintain surface temperatures above freezing. A lower limit to the time constant for accumulation of an amount of nitrogen equivalent to the present day value is 10 my if the outgassing were such as to provide a continuous surface mixing ratio of ammonia of at least 0.00001.

Kuhn, W. R.↗