The infrared chemiluminescence technique was applied to catalytic oxidation of CH₃OH, HCOOH and i-C₄H₁₀ on a Pd surface, and the reaction dynamics and mechanism were discussed in terms of internal energy states of nascent product CO₂ and CO molecules. The vibrational and rotational states of CO₂ produced by CH₃OH oxidation were quite similar to those of CO₂ produced by CO oxidation, indicating that the final step of the CO₂ formation in the CH₃OH oxidation involved a bimolecular process (i.e., CO_ad+O_ad). On the contrary, the intensity of IR emission of CO₂ produced by HCOOH oxidation was very weak, suggesting that most of CO₂ was not so vibrationally excited and that CO₂ was formed via decomposition of HCOO_ad (unimolecular decomposition of formate). The selective production of CO and H₂O was observed by the partial oxidation of i-C₄H₁₀ on Pd, and the vibrational state of product CO was very different between the Pd and Pt surfaces. These differences in internal energy states of the CO and CO₂ products can provide us with new information on the dynamics and mechanism of catalytic reactions.