Thermal decomposition of alkyl peroxynitrates

Abstract

X 1027 exp(-10766 K/F) molecule cm"3 is obtained for the equilibrium CH300N02 " CH300 + N02. Some experiments were performed on the thermal decomposition of isomeric mixtures of butyl, hexyl, and octyl peroxynitrate at 253 K and in 800 mbar of N2. Atmospheric implications of the thermal stability of alkyl peroxynitrates are briefly discussed.

Temperature and Pressure Studies of the Reactions of CH3O2, HO2, and 1,2-C4H9O2 with NO2

“…Plot of the experimental versus the MESMER calculated values for k -1 . The high values are from this study ( ) and Bridier et al 5 ( ) and the low values ( ) are from the nitrate decomposition studies of Zabel et al 7 The slope is equal to 1.007 ± 0.012, which indicates exceptional agreement. are in excellent agreement as shown in Figure 5, which is a correlation plot for the experimental and calculated rate constants.…”

“…More recently Jimenez et al 24 measured both  OH,PNA (0.09) and  HO2,PNA (0.89), which questioned the validity of the measurements of Macleod et al 22 1-,2-C 4 H 9 O 2 + NO 2 1-,2-C 4 H 9 O 2 NO 2 (3) , (-3) No studies have been carried out into the kinetics of the forward reaction, but measurements have been made for (CH 3 ) 3 CO 2 . 25 As with the other RO 2 NO 2 molecules in this study Zabel et al 7 has measured its decomposition kinetics.…”

“…Figure 4 and the results are given in Table 2. From Table 2 7 and Bridier et al 5 The total number of experimental values used in the fits was 63. The vibrational and rotational constants for each species were obtained from either experiment or the B3LYP/6-31+G** level of theory 47 and the newly formed bond RO 2 -NO 2 was treated as a hindered rotor.…”

“…[1][2] The RO 2 NO 2 species studied here are less stable than PAN but they play a significant role in the speciation of NO y . 6 completed a high pressure study, using an SF 6 bath gas with UV-Vis detection of CH 3 O 2 , which resulted in a much higher k 1  of 1.8 ×10 Zabel et al 7 have studied reaction (-1) using FTIR spectrometry to observe the decay of CH 3 O 2 NO 2 over the temperature range 245 -273K. These data, combined with the information on the forward reaction by Sander et al 3 and Ravishankara et al, 4 were used to calculate an enthalpy of dissociation of 92 kJmol -1 .…”

Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

“…Figure 3 shows the results of simulations for atmospheric trace species that yield NO 2 upon thermal dissociation under these conditions, with pressure reduction at point B. Rate constants were added for ClNO 2 (Baulch, et al, 1981;Knauth and Martin, 1978), BrONO 2 (Orlando & Tyndall, 1996), ClONO 2 (Anderson & Fahey, 1990), and CH 3 OONO 2 (Zabel, et al, 1989). The dissociation temperatures of these species have not been experimentally verified for this instrument, but it has been reported that nitryl chloride (ClNO 2 ) requires a higher temperature for dissociation than that normally used for measurement of PANs (Osthoff, et al, 2008).…”