Shock wave study and theoretical modeling of the thermal decomposition of c-C4F8. Issue 48 (18th November 2015)

• Record Type: Journal Article
• Authors: Cobos, C. J.; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; Troe, J.
• Is Part Of: Physical chemistry chemical physics. Volume 17:Issue 48(2015)
• Page Start: 32219
• Page End: 32224
• Publication Date: 2015-11-18
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c5cp05366h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The thermal dissociation of octafluorocyclobutane, c-C4 F8, was studied in shock waves over the range 1150–2300 K by recording UV absorption signals of CF2 . Abstract : The thermal dissociation of octafluorocyclobutane, c-C4 F8, was studied in shock waves over the range 1150–2300 K by recording UV absorption signals of CF2 . It was found that the primary reaction nearly exclusively produces 2 C2 F4 which afterwards decomposes to 4 CF2 . A primary reaction leading to CF2 + C3 F6 is not detected (an upper limit to the yield of the latter channel was found to be about 10 percent). The temperature range of earlier single pulse shock wave experiments was extended. The reaction was shown to be close to its high pressure limit. Combining high and low temperature results leads to a rate constant for the primary dissociation of k 1 = 10 15.97 exp(−310.5 kJ mol −1 /R T ) s −1 in the range 630–1330 K, over which k 1 varies over nearly 14 orders of magnitude. Calculations of the energetics of the reaction pathway and the rate constants support the conclusions from the experiments. Also they shed light on the role of the 1, 4-biradical CF2 CF2 CF2 CF2 as an intermediate of the reaction.