Fourier transform infrared spectroscopy was used to identify and quantify products of the self reaction of ethylperoxy radicals, C2H502, formed in the photolysis of C12/C2H6 mixtures in 700 torr total pressure of synthetic air a t 295 K . From these measurements, branching ratios for the reaction channelsof kIa/(kla + klb) = 0.68 and k l J ( k , a + klb + klJ 5 0.06 were established. Additionally, using the relative rate technique, the rate constant for the reaction of C1 atoms with C,H,OOH was determined t o be (1.07 t 0.07) x 10 lo cm3 molecule-' s-l. Results are discussed with respect to the previous kinetic and mechanistic studies of C2H502 radicals.
Reflection-absorption spectroscopy at grazing incidence has been shown to be a useful tool for investigation of thin organic films on gold and steel substrates. No artifacts related to the technique were identified for films thinner than 250 Å. The spectra obtained for films of an organic phosphate on polished steel substrates are consistent with reaction of the organic phosphate with the steel to produce a metal salt. The organic phosphate studied in this work was the reaction product of the diglycidyl ether of bisphenol-A (DGEBA), and comprised the mono- and diphosphoric acid adducts of DGEBA. The spectrum of the organic phosphate films formed on steel was indicative of a specific complex rather than the random product formed by bulk precipitation: the P-O stretching vibrations occurred as a pair of bands, while the spectrum of the salt formed from solution contained but a single band. No chemical interaction of the organic phosphate with the gold substrate was observed. The spectra have relative intensity changes with thickness which indicate the presence of ordering for the thinnest films studied.
FTIR spectroscopy has been shown to be a valuable tool in the analysis of complex gas phase mixtures, such as dilute vehicle exhaust. Regulated and non-regulated vehicle emissions have been routinely sampled and analyzed using prototype instrumentation developed in this laboratory, and in several other laboratories over the last decade.More recently, commercial versions of these FTIR analyzers have become available through several manufacturers. This paper reviews the data acquisition and processing techniques utilized by the FTIR analyzer developed in this laboratory. The statistical detection limits for 22 of the components analyzed by the system are presented. In addition, the linearity of the carbon monoxide (CO) analysis is demonstrated over several orders of magnitude. Experiments designed to study the effects of environmental parameters on the accuracy and the sensitivity of the system are also described.
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