Time resolved Fourier transform infrared (TRFTIR) emission has been used to study the reactions of CH 4 , C 2 H 6 , CH 3 F, CH 2 F 2 and CHF 3 with O( 1 D). One hundred and ninety-three nanomters photolysis of N 2 O was used to prepare O( 1 D), and emission analysed from OH(ν=1–4) for the two hydrocarbons and HF(ν=1–6) from CH 3 F, CH 2 F 2 and CHF 3 . For the O( 1 D)+CH 4 reaction, the nascent OH vibrational distribution showed a population inversion between ν=1 and 2, and was in excellent agreement with previous laser induced fluorescence and TRFTIR data, as well as with quasi-classical trajectory calculations. Time resolved populations were analysed to yield rate constants for vibrational relaxation of OH(ν) with CH 4 , and found to be consistent with stepwise deexcitation rather than chemical removal being dominant. Reaction with C 2 H 6 produced a monotonically decreasing population in ν=1–4 and more rapid relaxation rates than those with methane. For the fluorinated methanes, nascent vibrational populations in HF(ν=1–6) were measured and shown to be very similar, all monotonically decreasing with ν, and fitting the same vibrational surprisal plot, showing a larger than statistical partitioning of the available energy in vibration. Relaxation rate constants of HF(ν) with the parent fluorinated methane showed values, which increased with increasing H atom content.