OCR Text |
Show I Reaction II ~late Expression I Temp to achieve 4 nines destruction a. elimination (1,1 and 1,2) C2HsCI->C2H4+ HCI l.6xl013exp( -28400ff) 1008 C2HCIs->C2CI4+ HCI l.3xl013exp( -3 000 Off) 1072 C2HsF->~H4+ HF 2.5xl013exp( -30200ff) 1068 C2HF s- > C2F 4 + HF 4xl013exp( -36000ff) 1137 CF3H->CF2+HF l.3xl014xp( -36340ff) 1200 b. C-C bond cleavage CH3-CH3-> 2CH3 5xl016exp( -45000ff) 1242 CCI3-CCI3-> 2CCl3 6xl017 exp( -34400ff) 888 CF3-CF3->2CF3 l.Oxl0l7 exp( -45600ff) 1234 CF2=CF2->2CF2 2xl0uexp( -34700ff) 1050 c. C-X (H,CI,X) bond cleavage CH4->CH3+H 3.8xl0lsexp( -52400ff) 1557 ~CI6->C2CIs+Cl lxl0l6exp( -34500ff) 985 CF.->CFl+F 1.5xl0l7 exp( -64000fl) 1714 d.RadicalDecompostion CF2CF3->CF2+CFl 8xl0lsexp( -28100ff) 817 CF2CFl->CF1CF1+F 1. 7xl0l4exp( -36400fl) 1191 CFlCF1CF1->CFlCF1+CFlI4 lxl0l6exp( -26300ff) 759 CF2CF2CF3->CF1CF2+CFlI4 8xl013exp( -22700ff) 761 CH1CH3-> ~H4 + H 2xl013exp( -19540ff) 687 CH2CH1CH3-> CH1CH1+CH3 1.3xl013exp( -15200ff) 543 CCI2-CCI2CI-> CCl2CCI1 + CI 3xl013exp( -8960ff) 310 CH2-CH2CI-> CH2CH2 + CI 4xl0l3exp( -11180ff) 384 [able 2: Rate e xp resslons for unlD10lecuJar decom p oSitIon at the tu g: h p ressure 1lD11t At the high temperature combustion environment they will be subject to fall-off effects. Thus actual rate constants may be somewhat smaller. Except for those specifically marked, data have been derived from reference 4 and 6 less stable than the molecular analogs. Fluorinated radicals are however much more stable than the corresponding hydrocarbon or chlorinated hydrocarbon compounds. Furthermore, beta bond cleavage leading to the removal of a fluorine atom is not a favored channel. Indeed, the activation energy is so high that it probably never occurs. Instead contributions 10 |