The effect of the cold boundary layer on kinetic parameters was studied behind reflected shocks in a single pulse shock tube. By inserting hollow cylinders into the test section, parallel to the tube walls, the surface relative to the volume was increased, and the lowering of the chemical conversion was determined as a function of the surface per unit volume. The test reaction studied was the unimolecular decomposition of perfluorocyclobutane (C4F8→2C2F4). It was shown that the lowering of the chemical conversion was proportional to the surface-to-volume ratio in the test section. A hypothetical cold layer δc in which no conversion occurred was found to be around 0.2 mm. It was concluded that in a shock tube of ∼ 2-in. i.d., at an initial pressure of p1 ≥ 100 torr the cold boundary layer has very little effect on kinetic parameters obtained in a single-pulse shock tube. At lower pressures and in smaller diameters shock tubes these effects should be considered when interpreting kinetics results.