Experimental and computational investigation of gas-phase reaction of chlorine with n-propanol: observation of chloropropanol conformational isomerization at room temperature.

FTIR smog chamber techniques were used to measure k(Cl+n-C3H7OH) = (1.74 +/- 0.15) x 10-10 and k(Cl+CH2ClCH2CH2OH) = (7.54 +/- 0.73) x 10-11 cm3 molecule-1 s-1 in 700 Torr of N2 at 296 K. The reaction of Cl with n-C3H7OH gives CH3CH2CHOH, CH3CHCH2OH, and CH2CH2CH2OH radicals in yields of 60 +/- 5, 25 +/- 8, and 15 +/- 3%, respectively. Neither CH3CH2CHClOH nor CH3CHClCH2OH is available commercially, and infrared spectra for the three chlorides CH3CH2CHClOH, CH3CHClCH2OH, and CH2ClCH2CH2OH were calibrated experimentally. MP2/6-31G(d,p) calculations were used to corroborate the experimental vibrational assignments. Analysis reveals that each geometric isomer possesses several structurally and spectroscopically distinct conformers arising from intramolecular hydrogen bonding and, in the case of CH3CH2CHClOH, negative hyperconjugation. These conformers interchange slowly enough to be distinguished within the room-temperature vibrational spectrum. The experimentally observed vibrational spectra are well described by a Boltzmann-weighted superposition of the conformer spectra. As is typical of alpha-halogenated alcohols, CH3CH2CHClOH readily decomposes heterogeneously to propanal and HCl.