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Photodissociation of the group VIB (Cr,Mo,W) hexacarbonyls has been studied at 248 nm using molecular beam photofragment spectroscopy. One, two and three photon processes have been observed. Analysis of the product velocity distributions shows that the photodissociation mechanism consists of sequential CO eliminations with the nth photon channel best described as the single photon photodissociation of the stable products of the n-1st photon channel. The product translational energy distribution for the first CO elimination step is quantitatively similar for all three hexacarbonyls and characteristic of a repulsive translational energy release. The product translational energy distributions of all subsequent CO elimination steps are accurately described by a simple, microcanonical model. Qualitative molecular orbital considerations suggest that the large product translational energy observed in the first CO elimination step results from a repulsive σ interaction between the closed shell CO ligand and an excited molecular orbital which has a significant admixture of metal (n+1)pz, (n+1)s and ndz2 orbitals. This repulsive interaction is absent in the remaining CO elimination steps because there are vacancies in the coordination shell along the z axis. [ABSTRACT FROM AUTHOR]

A molecular beam of zinc–diethyl (ZnEt2) is photodissociated at 248 and 193 nm and the velocity distributions of the photofragments are measured by time-of-flight techniques. One and two photon processes are observed. The dominant one photon process at both wavelengths is the dissociation of (ZnEt2)2 to form two ZnEt2 monomers. The absence of secondary dissociation of the ZnEt2 photofragments at both excitation wavelengths and the small fraction of the available energy partitioned to product translation implicates dissociation to an excited electronic potential energy surface correlating to one electronically excited ZnEt[ATOTHER]@B|[/ATOTHER]2 monomer. The mass spectrum of the ZnEt2 photofragments is the same as measured for ‘‘cold’’ ZnEt2 monomers in the molecular beam, suggesting that the electronically excited ZnEt[ATOTHER]@B|[/ATOTHER]2 monomers have fluoresced prior to ionization in the mass spectrometer. A small photodissociation signal of uncomplexed ZnEt2 is observed only at low expansion pressures. The sensitive dependence of this monomeric photodissociation signal to the Ar pressure of the adiabatic expansion suggests that ground state vibrational excitation is required for monomeric photodissociation at 248 nm.In contrast to the dimer single photon photodissocation channel, when ZnEt2 monomers are photodissociated, a significant fraction of the available energy appears as product translation. A qualitative molecular orbital analysis can explain the observed fast photoproduct velocity if dissociation occurs via a repulsive triplet state which correlates to electronic ground state products. The two photon process observed is assigned to single photon photodissociation of the electronically excited ZnEt[ATOTHER]@B|[/ATOTHER]2 monomers produced in the dimer photodissociation step. The photofragment velocity distributions for the two photon channel can be quantitatively modeled by sequential ethyl eliminations on... [ABSTRACT FROM AUTHOR]

A crossed laser-molecular beam study of the one and two photon dissociation mechanism of bis (cyclopentadienyl) iron (ferrocene, FeCp2) has been performed at 193 and 248 nm. By combining electron bombardment mass spectroscopy with time-of-flight (TOF) measurements, the photodissociation mechanism at 193 nm is shown to have two distinct mechanisms. (1) FeCp2+hν→FeCp*+Cp; (2) FeCp+2hν→FeCp+Cp, FeCp→Fe+Cp. For the first mechanism, which accounts for less than 5% of the photodissociation events, the FeCp* velocity distribution is quantitatively consistent with a statistical dissociation producing FeCp in an excited, ligand field electronic state. The velocity distributions of the Cp and Fe fragments produced by the second mechanism (FeCp is an unstable intermediate) are also in excellent agreement with microcanonical calculations for both Cp elimination steps using the known metal–ligand bond energies of ferrocene. For the second mechanism, dissociation occurs on the lowest potential energy surface for each Cp elimination. Although one photon is energetically sufficient to remove one Cp ligand from ferrocene, RRKM calculations of the lifetime indicate that Cp elimination is extremely slow for dissociation along the ground electronic state potential energy surface. Hence, after internal conversion to the ground electronic state, the large photon absorption cross section (∼4 Å2) for the experimental irradiation conditions allows additional photons to be absorbed until the dissociation rate exceeds the up pumping rate. The large photon energy causes the dissociation rate to increase by many orders of magnitude for each additional photon absorbed. Consequently, there is strong selectivity for the total number of photons absorbed. Both mechanisms, occurring on two different electronic potential energy surfaces, suggest that dissociation induced by excitation of the ligand-to-metal charge transfer states accessed at 193... [ABSTRACT FROM AUTHOR]

A combined plasma photolysis (CPP) reactor that utilizes a dielectric barrier discharge (DBD) plasma and 207nm UV radiation from discharge-driven KrBr∗ excimers was designed and constructed. Gas streams containing CS2 were treated with stand-alone DBD and CPP at atmospheric pressure. In comparison to DBD, CPP greatly enhanced the removal efficiency at the same applied voltage, waste gas concentration and gas residence time. Thus the applied voltage could be reduced to a certain extent in the plasma processing of industrial wastes. Influences of the KrBr∗ radiation, inlet CS2 concentration and gas residence time on CS2 removal by CPP were also studied. In addition, the likely reaction mechanisms for the removal of CS2 by CPP are suggested based on the byproducts analysis. The enhanced removal efficiency and reaction mechanisms implied that the CPP process would probably be suitable for the removal of a large number of gaseous pollutants. [Copyright &y& Elsevier]

Abstract: The reaction mechanism of 3-chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3-chlorophenol aqueous solutions have been saturated with air or N[sub 2] previously. Under alkaline condition, the reaction of OH radical with 3-chlorophenol produces 3-chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3-chlorophenol produces OH-adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3-chlorophenol produces H-adduct with the maximal absorption at about 320 nm. 3-chlorophenol is compared with 4- and 2-chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process. [ABSTRACT FROM AUTHOR]

A molecular beam study of the Cl2+GaAs(s) reaction has been performed for surface temperatures in the range of 300–550 K. The gas phase neutral reaction products are identified by mass spectroscopy using electron bombardment ionization. Detailed analysis of the surface temperature dependence of the mass spectrum of the observed reaction products indicates that only three neutral reaction products are formed in this temperature range: GaCl3, AsCl3, and As4. At low (high) surface temperatures, only AsCl3 (As4) is observed. The ratio of the etching rates of Ga and As is independent of the surface temperature and within the range expected for stoichiometric etching. The change in the mode of As removal with surface temperature for the incident Cl2 flux implies that surface diffusion is important at surface temperatures above 400 K. [ABSTRACT FROM AUTHOR]

Abstract: The photolysis of simulating low concentration of hydrogen sulfide malodorous gas was studied under UV irradiation emitted by self-made microwave discharge electrodeless lamps (i.e. microwave UV electrodeless mercury lamp (185/253.7nm) and iodine lamp (178.3/180.1/183/184.4/187.6/206.2nm)). Experiments results showed that the removal efficiency () of hydrogen sulfide was decreased with increasing initial H2S concentration and increased slightly with gas residence time; H2S removal efficiency was decreased dramatically with enlarged pipe diameter. Under the experimental conditions with pipe diameter of 36mm, gas flow rate of 0.42standardls−1, was 52% with initial H2S concentration of 19.5mgm−3 by microwave mercury lamp, the absolute removal amount (ARA) was 4.30μgs−1, and energy yield (EY) was 77.3mgkWh−1; was 56% with initial H2S concentration of 18.9mgm−3 by microwave iodine lamp, the ARA was 4.48μgs−1, and the EY was 80.5mg kWh−1. The main photolysis product was confirmed to be with IC. [Copyright &y& Elsevier]

The reaction mechanism of O3 with bromide ion in aqueous solution was studied by ion chromatography and UV-Vis spectrometry instruments. Ion chromatography analysis showed that only 10% of Br- which was oxidized by ozone was formed into bromate ion. The results demonstrated that the final products of the oxidation reaction were identified as Br2 and Br3- except for BrO3-. The formation of Br3- which was yielded from the reaction of Br2 with Br- was the major process in the reaction of Br attacked by O3. The characteristic absorption spectrum of Br3- with an absorption peak at 260 nm was also investigated. The results may provide helpful information about the mechanism of the oxidation reaction of Br- with O3 and fate of Br- or its derivatives in the environment by the oxidation processes.

The photolysis of simulating carbon disulfide malodorous gas was studied under UV irradiation emitted by microwave electrodeless lamps. Experiments results show that the photolysis of carbon disulfide is determined by the initial concentration, residence time and gas humidity. When air velocity is 0.2 m/s, initial concentration is about 100 mg/m3, and gas humidity is about 40%, the conversion ratio of carbon disulfide can reach to 75% with microwave electrodeless mercury lamp and 50% with microwave electrodeless iodine lamp. The mechanism of carbon disulfide photolysis was further studied. It is concluded that the photolysis of carbon disulfide is probably a collective action of direct photolysis and *OH radical oxidation.

The 355 nm photon-initiated microscopic reaction mechanisms of the mixed aqueous solution of nitrobenzene and nitrous acid in the presence or absence of O(2) were studied by the laser flash photolysis technique. The main transient absorption peaks in the recorded spectra were assigned and the growth/decay trends of several transient species were investigated. It was found that the OH radical formed from the photolysis of nitrous acid triggered most of the subsequent radical reactions. The rate constant of the reaction between OH radical and nitrobenzene was measured to be (3.4 +/- 0.1) x 10(9) l mol(-1) s(-1). The product from this reaction, namely C(6)H(5)NO(2)-OH adduct, was found to react with O(2) to yield C(6)H(5)NO(2)-OHO(2) adduct with a rate constant of (1.6 +/- 0.2) x 10(9) l mol(-1) s(-1). Final steady-state products were identified by GC/MS analysis and were in accordance with the transient spectroscopic results. The possible reaction pathways were proposed.

We verified that C6F6, a typical perfluorine compound, could be photocatalytic degraded by H3PW12O40. The defluorination of C6F6 was determined as a function of irradiation time, pH, initial concentration of H3PW12O40, and additives as well. The defluorination of C6F6 increased with the irradiation time. Acid condition, especially pH = 1.0 is preferred. 3 mL solution of 2.0 x 10(-4) mol/L C6F6 and 5.0 x 10(-6) mol/L H3PW12O40 was irradiated for 20 min and the defluorination of C6F6 was equal to 208.1%. O2, KMnO4 and K2S2O8 added in the solution were able to increase the defluorination of C6F6 via oxidating [PW12O40](4-). The defluorination of C6F6 would decline in the presence of alcohol and aromatic compounds.

SF5CF3 was identified recently as a potent greenhouse gas with strong radiative force and long atmosphere residential life. Spark discharge method was used to take simulative investigation on the elimination of SF5CF3 from atmosphere under discharge here. The results show that SF5CF3 was dissociated under discharge and formed some compounds containing S, F, O and C. The dissociation of SF5CF3 was reduced if the system existed H2O, but it was independent of the amount of H2O. The rate coefficients were estimated to be 0.011s(-1) under moisture circumstance when the system total pressure was about 31 kPa. And the increase of the system pressure would cause exponential decrease of SF5CF3 dissociation. The reactive mechanism was argued based on the experiment results and the sinks of SF5CF3 under lightning (one of the discharge in the atmosphere) was estimated to be 53.6 kg x a(-1).

The rate constants of reactions between the SO4*(-) radical and some common anions in atmospheric aqueous droplets e.g. Cl-, NO3-, HSO3- and HCO3- were determined using the laser flash photolysis technique. Absorption spectra of SO4*(-) and the product radicals were also reported. The chloride ion was evaluated among all the anions to be the most efficient scavenger of SO4*(-). The results may supply useful information for a better understanding of the vigorous radical-initiated reactions in atmospheric aqueous droplets such as clouds, rains or fogs.