Abstract
The infrared multiple-photon single-frequency decomposition (IRMPD) of CBrClF2 was examined as functions of laser wavenumber, laser fluence, and partial pressure of CBrClF2. The initial step was the scission of a C-Br bond. In the presence of O2 the carbon-containing product was CF2O and its subsequent hydrolysis gave CO2. The initial dissociation was highly 13C selective at wavenumbers below 1014 cm−1. CBrClF2 decomposed at relatively low fluences as compared to CHClF2. However, the decomposition yield rapidly decreased with increasing pressure. In the large-scale irradiation experiment using about 8 J pulse at 1 Hz, we obtained a carbon yield of 0.41 μmol per pulse at a 13C-atom fraction of 17% for a mixture of 10 Torr CBrClF2 and 10 Torr O2, and a carbon yield of 0.17 μmol per pulse at a fraction of 29% for a mixture of 20 Torr CBrClF2 and 20 Torr O2. The IRMPD of CHClF2 gave a carbon yield of 0.18 μmol per pulse at 48% for 10 Torr neat CHClF2 and yield of 0.25 μmol at 52% for 20 Torr CHClF2. The large-scale irradiation experiment was also carried out for mixtures of CBr2F2 and O2. CHClF2 is the most productive of 13C.
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The relation between a beam cross section y (cm2) and distance x (cm) from a lens is roughly expressed by the following equation: y=(2.9x 2/15000)−(6.96x/100)+8.00. The position of the cell is x=60 at the front and x=260 at the exit. The following experimental relations can be derived from Fig. 5 (the laser line used, 9P(30)): log10 12Pd=1.40F−6.95, log10 13Pd=1.00F−4.34, where F is the fluence (J cm−2).
The photolysis zone was decomposed into 200 pieces with a thickness of 1 cm along the beam direction. The 12C and 13C yields per pulse correspond to \(\sum\limits_i {^{12} P_d } \cdot y^i \cdot [^{12} CBrClF_2 ] and \sum\limits_i {^{13} P_d } \cdot y^i \cdot [^{13} CBrClF_2 ]\), respectively. The carbon yields may increase slightly and the 13C-atom fraction decreases in the 9P(28) line of Table 1
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Hattori, M., Ishikawa, Y., Mizuta, K. et al. 13C-selective infrared multiple-photon decomposition study of CBrClF2 . Appl. Phys. B 55, 413–418 (1992). https://doi.org/10.1007/BF00325179
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DOI: https://doi.org/10.1007/BF00325179