Thermal decomposition of phosgene

摘要: The thermal decomposition of COCl[sub 2] has been studied in incident shock waves at three different loading pressures and varying [COCl[sub 2]][sub 0]. kinetics experiments were performed temperatures between 1400 2000 K by monitoring the product Cl atoms using atomic resonance absorption spectrometric (ARAS) technique. Two pathways for are possible: (1) (+M) [yields] COCl + (2) CO Cl[sub (+M). branching ratios observed to be 90[sub .5]% 9[sub .5]%, respectively. Second-order analysis sum gave rate expression k[sub d]/[Kr] = (8.0 [+-] 3.8) x 10[sup [minus]8] exp(-30549 766 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1], with an error 35% one standard deviation level. This compares favorably results from decompositions CH[sub 3]Cl, 2]Cl[sub 2], CCl[sub 4] provides evidence suggest that [Delta]H[sup [circ]][sub 10] is range 70-80 kcal mol[sup [minus]1]. Theoretical also applied reaction 1 Troe's semiempirical methods. best overall fit obtained 74.5 1.0 [minus]1]more » [Delta]E[sub down] 1714 implies [Delta][sub f]H[sup [circ]](0 K) -6.3 -1] COCl. Similar theoretical 2 suggests a barrier height 81.35 [minus]]. 31 refs., 4 figs., 3 tabs.« less