The thermal decomposition of propane has been studied using both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for propane have been measured at high temperatures behind reflected shock waves using high-sensitivity H-ARAS detection and CH(3) optical absorption. The two major dissociation channels at high temperature are C(3)H(8) -> CH(3) + C(2)H(5) (eq 1a) and C(3)H(8) -> CH(4) + C(2)H(4) (eq 1b). Ultra high-sensitivity ARAS detectior of H-atoms produced from the decomposition of the product, C2H5, in (la), allowed measurements of both the total decomposition rate constants, k(total), and the branching to radical products, k(1a)/k(total). Theoretical analyses indicate that the molecular products are formed exclusively through the roaming radical mechanism and that radical products are formed exclusively through channel la. The experiments were performed over the temperature range 1417-1819 K and gave a minor contribution of (10 +/- 8%) due to roaming. A multipass CH(3) absorption diagnostic using a Zn resonance lamp was also developed and characterized in this work using the thermal decomposition of CH(3)I as a reference reaction. The measured rate constants, for CH3I decomposition agreed with earlier determinations from this laboratory that were;based on I-atom ARAS measurements. This CH3 diagnostic Was then used to detect radicals from channel la allowing lower temperature (1202-1543 K) measurements of k(1a) to be determined. Variable reaction coordinate transition state theory. was used to Predict the high pressure limits for Channel (la) and other bond fission reactions in C(3)H(8). Conventional transition state theory calculations were also used to estimate rate constants for other tight transition state processes. These calculations predict a negligible contribution (< 1%) from all other bond fission and tight transition state processes, indicating that the bond fission channel (1a) and the roaming channel (1b) are indeed the only active channels at the temperature and pressure ranges of the present experiments. The predicted reaction exo- and endothermicities are in excellent agreement with the current version of the Active Thermochemical Tables. Master equation calculations incorporating these transition state theory results yield predictions for the temperature and pressure dependence of the dissociation rate constants for channel 1a. The final theoretical results reliably reproduce the measured dissociation rate constants that are reported here and in the literature. The experimental data are well reproduced over the 500-2500 K and 1 x 10(-4) to 100 bar range(errors of similar to 15% or less) by the following Troe parameters for Ar as the bath gas: k(infinity) = 1.55 x 10(24)T(-2.034) exp (-45 490/T) s(-1), k(0) = 7.92 x 10(53)T(-16.67) exp(-50 380/T) cm(3)s(-1), and F(c) = 0.190 exp (-T/3091) + 0.810 exp(-T/128) + exp(-8829/T).