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This work describes an experimental and numerical investigation of the thermal transient of i.c. engine exhaust systems. A prototype of exhaust system has been investigated during a NEDC cycle in two different configurations. Firstly an uncoated catalyst has been adopted to consider only the effect of the gas-wall heat transfer. The measurements have been repeated on the same exhaust system equipped with a coated catalyst to point out the contribution of the chemical reactions to the thermal transient of the system. The measured values have been compared to the predicted results carried out with a 1D thermo fluid dynamic code, developed in-house to account for the thermal transient of the system and the chemical reactions occurring in the catalyst.