The decomposition of cyclohexane (c-C₆H₁₂) was studied in a shock tube using the laser-schlieren technique over the temperature range 1300−2000 K and for 25−200 Torr in mixtures of 2%, 4%, 10%, and 20% cyclohexane in Kr. Vibrational relaxation of the cyclohexane was also examined in 10 experiments covering 1100−1600 K for pressures below 20 Torr, and relaxation was found to be too fast to allow resolution of incubation times. The dissociation of 1-hexene (1- C₆H₁₂), apparently the sole initial product of cyclohexane decomposition, was also studied over 1220−1700 K for 50 and 200 Torr using 2% and 3% 1-hexene in Kr. On heating, cyclohexane simply isomerizes to 1-hexene, and this then dissociates almost entirely by a more rapid C−C scission to allyl and n-propyl radicals. This two-step reaction results in an initial small density gradient from the slight endothermicity of the isomerization. The gradient then rises strongly as the product 1-hexene dissociates. For the lower temperatures, this behavior is fully resolved here. For the higher pressures, 1-hexene decomposition generates negative gradients (exothermic reaction) as the radicals formed begin to recombine. Cyclohexane also generates such gradients, but these are now much smaller because the radical pool is depleted by abstraction from the reactant. A complete mechanism for the 1-hexene decomposition and for that of cyclohexane involving 79 reactions and 30 species is used in the final modeling of the gradients. Rate constants and RRKM fit parameters for the initial reactions are provided for the entire range of conditions. The possibility of direct reaction to allyl and n-propyl radicals, without stabilization of the intermediate 1-hexene, is examined down to pressures as low as 25 Torr, without a clear resolution of the issue. High-pressure limit rate constants from RRKM extrapolation are k_∞(c-C₆H₁₂ → 1-C₆H₁₂) = (8.76 × 10¹⁷) exp((−91.94 kcal/mol)/RT) s⁻¹ (T = 1300−2000 K) and k_∞(1-C₆H₁₂ → ^•C₃H₇ + ^•C₃H₅) = (1.46 × 10¹⁶) exp((−69.12 kcal/mol)/RT) s⁻¹ (T = 1200−1700 K). This high-pressure rate for cyclohexane is entirely consistent with the notion that the isomerization involves initial C−C fission to a diradical. These extrapolated high-pressure rates are in good agreement with much of the literature.

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