Rates and pathways of the reactions and processes at the surface of burning energetic materials, such as explosives and propellants, are very difficult to measure experimentally. A "snapshot" simulation of the surface reaction zone is captured by a thin layer of material heated rapidly to temperatures characteristic of the burning surface. By the use of T-jump/FTIR spectroscopy, kinetics and heat changes can be determined during this event, and the early-stage chemistry can be assembled from the gaseous products of decomposition. Results for ammonium nitrate, poly(butadiene) polymers, hydrazinium nitroformate, and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazacine (HMX) illustrate progress in this field.