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- W2014806489 abstract "Abstract Absolute reaction rate constants for the ground state dichlorocarbene CCl2 with C2H2 and H2O have been measured (T=293 K). The CCl2 radicals were produced by laser photolysis of CCl4 molecules at 213 nm and then electronically excited to the CCl2 ( A ) state at 541.0 nm with Nd:YAG laser pumped dye laser. The technique of laser-induced fluorescence was employed to measure the relative concentrations at different reaction time and, then, obtain their rate constants. They are (3.3 ± 0.5) × 10−13 cm3 molecule−1 s−1 for the reaction of CCl2 + C2H2 and (4.8 ± 2.0) × 10−14 cm3 molecule−1 s−1 for the reaction of CCl2 + H2O (total pressure=12 Torr, T=293 K), respectively. It is found that the rate constant for reaction CCl2 + C2H2 slightly increases with the total pressure (P=10–50 Torr). But for the reaction CCl2 + H2O, it is independent on the total pressure. The mechanisms for these two reactions have been theoretically studied using a high-level ab initio calculation. For the reaction of CCl2 + H2O, it is found that there are two reaction mechanisms: insertion and addition-elimination. Three primary product channels, HCl + HClCO, HCl + trans-ClCOH and HCl + cis-ClCOH, are studied in detail. For the reaction of CCl2 + C2H2, there are also two reaction mechanisms: insertion and three-cyclo-addition. The addition of C atom in CCl2 radical to C–C triple bond in C2H2 molecule may be the dominant reaction channel giving a three-member-ring structure, CCl2 CHCH radical, as the primary intermediate." @default.
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- W2014806489 date "2004-08-01" @default.
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- W2014806489 title "Reaction kinetic studies of CCl2 (X̃(0,0,0)) with C2H2 and H2O molecules" @default.
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- W2014806489 doi "https://doi.org/10.1016/j.chemphys.2004.06.016" @default.
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