By D. W. Setser
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Extra info for Reactive Intermediates in the Gas Phase. Generation and Monitoring
A. CLYNE A N D WING S. NIP DiP 2 3s-2p 4s-2p 5 I I S " 5 PJP r m 2 4 g 95 96 82 nm P- P I I 3s-2p> 2 II I o> cm u->r9> o> I 97 98 nm Fig. 1 0 . Emission spectrum of F atom resonance lamp. 4 Torr. 25-W incident microwave power. Note self-reversal between P and P lines. 1-m normal-incidence spectrometer, first order of 600 line/mm grating blazed at 90 nm, 5 fxm slits. ] 2 2 2 3 / 2 1 / 2 (generally referred to as single-stage sampling system) based on the design by Eltenton (1947) is not suitable for quantitative measurements of atom and radical concentrations.
Particularly suitable labile molecules for detection with high sensitivity include: O H , SO, C N , and N H radicals in the ultraviolet and N H , P H , B 0 , IF, and BrF in the visible regions. N 0 , 1 Br , C l , BrCl, IC1 are examples of stable molecules whose sensitive detection by laser induced fluorescence can be very useful in discharge-flow kinetics. W o r k up to about 1975 has been reviewed by Walther (1976). Typical more recent literature citations include: McAfee and Hozack (1976) and Clyne and McDermid (1976, 1977, 1978a-d).
1970; Davis et ai, 1970; Deakin and Husain, 1972; Husain and Kirsch, 1971; Husain and Norris, 1977). Although both the Doppler model and the Biondi model will reduce to a Beer-Lambert relationship with y = 1 when A -> 0 (Bemand and Clyne, 1973a; Clyne and Smith, y 10 0 32 MICHAEL A. A. CLYNE A N D WING S. NIP 1978), there is no theoretical justification for the modified form, and the exponent y is an empirical parameter which depends on both the lamp characteristics and on the range of absorbance under consideration.