The decomposition of carbonyl fluoride (COF2), the reactions of carbonyl fluoride with carbon monoxide (CO), and the reactions of carbonyl fluoride with hydrogen (H2) in excess argon were studied behind reflected shock waves. Kinetic data were obtained in the temperature and total pressure ranges 2600–3300 °K and 2.5–9.0 atm, respectively, for the COF2 decompostion study, in the temperature and total pressure ranges 2400–3000 °K and 3.3–7.7 atm, respectively, for the COF2–CO study, and in the temperature and total pressure ranges 1900–2700 °K and 2–12 atm, respectively, for the COF2–H2 study. Under the experimental conditions, the bimolecular reaction between COF2 and CO was found to be negligible with respect to the decomposition of COF2. An empirical relationship for the over-all kinetics of the COF2–H2 reaction was determined, and a combined analytical and experimental study was conducted to determine a plausible mechanism for the COF2–H2 reaction. Under the experimental conditions, the dominant reaction steps in this mechanism were determined to be COF2+M →k1 COF+F+M, COF+M →k2 CO+F+M, H2+M → H+H+M, F+H2 → HF+H, H+COF2 →18 COF+HF, H+COF →20 CO+HF. In these studies an experimental value of k1 was obtained as k1 = 1014.25±0.24 exp(−77 200 ± 3300/RT) cc/mole⋅sec. The rate constant for Reaction 2 was derived based on experimental data, a steady state analysis, and an estimate of the ratio of the rate constants of Reactions 18 and 20. The derived value for k2 is given as k2 = 1015.0 exp(−49 000/RT) cc/mole⋅sec. The heat of formation of COF at absolute zero was determined to be approximately equal to −66 kcal/mole relative to the JANAF standard state definition.
The thermal decomposition of methyl nitrite (CH,ONO), in excess argon, CH,ONO + M -+ CH,O + NO + M, was studied behind both incident and reflectedshock waves. Kinetic data were obtained in the temperature and total pressure ranges 715-1118 OK and 0.8-5 atmospheres, respectively. The reaction was found to be unimolecular in nature and occurring in the low pressure region, with a rate constant expression, k = 10"·30±O.aa exp( -30,400 ± 850fRT), cc/mole-sec.: giving the best least-squares fit to the data. Treatment of the data with R.R.K. theory leads to the conclusion that I!J.H;OR.O~9.0 kcalfmole rather than the present literature value of 3.5 kcal/rnole. The results of previous investigators are compared to the present findings. The molecular absorption coefficient of methyl nitrite at 2800 ± 30 A was found to be temperature dependent. The values of the absorption coefficient was fit to the form, e~300±'OA = 636T -229,010 ccfrnole-cm.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.