Kinetic and modeling studies on ETBE pyrolysis behind reflected shock waves

The high temperature pyrolysis of ethyl tert-butyl ether (ETBE) was studied behind reflected shock waves coupled with the single-pulse method and UV (195 nm) absorption spectroscopy in the temperature range 1000-1500 K at total pressures ranging between 1.0 and 9.0 atm. The energies of ETBE and transition states for the reactions ETBE = iso-C ₄H ₈ + C ₂H ₅OH (1) and ETBE = C ₂H ₄ + tert-C ₄H ₉OH (2) were calculated at the MP4/cc-pVTZ//MP2/cc-pVTZ level of theory. A 170-reaction mechanism was constructed to explain the product distribution. From the UV absorption experiment, the rate coefficient k₁ = 1.7 × 10 ¹⁴exp(-254.0 kJ mol ^-1/RT) s ^-1 was found to reach its high-pressure limit.