Shock Tube Study on the Thermal Decomposition of n-Butanol

Dilute concentrations of normal-butanol has been decomposed in single pulse shock tube studies in the presence of large quantities of a chemical inhibitor that suppresses contributions from chain decomposition. Reaction temperatures and pressures are in the range of [1126-1231] K and [1.3-6.5] bar. Ethylene and 1-butene are the only products. The mechanism of the initial decomposition steps involves direct elimination of water and C-C bond cleavage. The fundamental high pressure unimolecular decomposition rate expressions are k(C4H9OH -> CH3 + CH2CH2CH2OH) = 10(16.4 +/- 0.4) exp(42410 +/- 800 [K]/T) s(-1); k(C4H9OH -> CH3CH2 + CH2CH2OH) = 10(16.4 +/- 0.4) exp(-41150 +/- 800 [K]/T) s(-1); k(C4H9OH -> CH3CH2CH2 + CH2OH) = 10(16.4 +/- 0.4) exp(-41150 +/- 800 [K]/T) s(-1); and k(C4H9OH -> CH3CH2CH=CH2 + H2O) = 10(14.0 +/- 0.4) exp (-35089 +/- 800 [K]/T) s(-1), where the rate expressions for C-C bond cleavage are based on assumptions regarding the relative rates of the three processes derived from earlier studies on the effect of an OH group on rate expressions. All reactions are in the high pressure limit and suggest that the step size down in the presence of argon is at least 1300 cm(-1). These rate expressions are consistent with the following H-C bond dissociation energies: BDE(H-CH2CH2CH2OH) = 417.2 +/- 7 kJ/mol, BDE(H-CH2CH2OH) = 419.2 +/- 7 kJ/mol, and BDE(H-CH2OH) = 401.7 +/- 9 kJ/mol, with an estimated uncertainty of 6 kJ/mol. The kinetics and thermodynamic results are compared with estimates used in the building of combustion kinetics databases.