Journal of Physical Chemistry A, Vol.108, No.8, 1417-1424, 2004
Kinetic studies on the reactions of heptafluoropropanes with O(P-3) and H atoms at high temperatures
The reactions of 2H-heptafluoropropane (CF3CHFCF3, HFC-227ea) with O(P-3) and H atoms have been studied at high temperatures by using a shock tube technique coupled with atomic resonance absorption spectroscopy. Electronically ground-state oxygen and hydrogen atoms were produced by the laser photolysis of sulfur dioxide and the thermal decomposition of ethyl iodide, respectively. The rate coefficients for the reactions CF3CHFCF3 + O(P-3) --> i-C3F7 + OH (1a) and CF3CHFCF3 + H --> i-C3F7 + H-2 (2a) were experimentally determined from the decay of O(P-3) and H atoms as k(1a) = 10(-10.27+/-0.67) exp[-(56 +/- 13) kJ mol(-1)/RT] cm(3) molecule(-1) s(-1) (880-1180 K) and k(2a) = 10(-9.15+/-0.66) exp[-(63 +/- 14) kJ mol(-1)/RT] cm(3) molecule(-1) s(-1) (1000-1180) K). These results showed that reaction 2a was faster than reaction 1a by a factor of 7-8 over the present experimental temperature range. Both rate coefficients were much smaller than the previous kinetic data for the reactions of propane with O(P-3) and H atoms, because of an electron-attracting effect of fluorine atoms. To compare the reactivities between isomers, the rate coefficients for the reactions of 1H-heptafluoropropane, CHF2CF2CF3 + O(P-3) --> n-C3F7 + OH (3a) and CHF2CF2CF3 + H --> n-C3F7 + H-2 (4a), were also determined by using the same technique as k(3a) = 10(-10.13+/-0.52) exp[-(55 +/- 10) kJ mol(-1)/RT] cm(3) molecule(-1) s(-1) (880-1180 K) and k(2a) = 10(-9.44+/-0.32+/-) exp[-(57 +/- 7) kJ mol(-1)/RT] cm(3) molecule(-1) s(-1) (1000- 1180 K). Furthermore, the rate coefficients for reactions 1a and 2a were calculated with the transition state theory (TST). Structural parameters and vibrational frequencies of the reactants and the transition states required for the TST calculation were obtained from the MP2(full)/6-31G(d) ab initio molecular orbital (MO) calculation. The energy barrier, E-0(double dagger), was adjusted until the TST rate coefficient most closely matched the observed one. The fitting results of E-0(double dagger)(1a) = 51 W mol-I and E-0(double dagger)(2a) = 41 kJ mol(-1) were in agreement with the G2(MP2) energy barriers, within the expected uncertainty.