Ionization and dissociation of nitrosyl chloride CINO were studied using femtosecond laser mass spectra technique. Strong fragmental ions NO^＋ and Cl^＋ were observed with the laser intensity varied from 3.2× 10^14 to 2.5×10^15 W/cm^2. These fragmental ions were attributed to the direct dissociation of the parent ions. Electronic structure calculations were also carried out with Hartree-Fock, density functional and correlated levels of theory to understand the possible fragmentation pathways. The very low N-Cl bond energy in the parent ion of nitrosyl chloride is a clear reason for the absence of CINO^＋ and CIN^＋ ion peaks from the femtosecond laser mass spectrum.
Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.
The short-lived reactive specimen nitrous acid HONO was generated in the gas phase by the hetero-geneous reaction of gaseous HCl with AgNO2 which can generate higher concentration of HONO than other methods. We investigated the process from generation to dissociation in the gas phase under different controlled temperatures,and discussed the ionization and reaction on the solid surface by combination of the photoelectron spectroscopy and photoionization mass spectroscopy(PES-PIMS) and in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) .
The importance of the iodine chemistry in the atmosphere has been demonstrated by recent observa- tions. The uptake of ethyl iodine on black carbon surface was investigated at 298 K for the first time. Degussa FW2 (an amorphous black carbon comprising medium oxides) was used as black carbon sample. Black carbon surface was found to be deactivated in reaction with C_2H_5I, and the uptake coef- ficient (γ ) was dependent on the time of exposure. The value of (2.3±0.9)×10^(-2) was determined for the initial uptake coefficient (γ0). The result suggests that the heterogeneous loss of C_2H_5I on carbonaceous aerosols may be important under the atmospheric conditions.
