Currently, the pyrolysis process is an important technology for the final treatment of plastic waste worldwide. For this reason, knowing in detail the chemical process and the thermodynamics that accompany cracking reactions is of utmost importance. The present study aims to determine the thermodynamic parameters of the degradation process of conventional thermoplastics (polystyrene (PS), polyethylene terephthalate (PET), high-density polyethylene (HDPE), polypropylene (PP) and polyvinyl chloride (PVC)) from the study of their chemical kinetics by thermogravimetric analysis (TG). Non-isothermal thermogravimetry was performed at three heating rates from room temperature to 550 °C with an inert nitrogen atmosphere with a flow of 20 mL min−1. Once the TG data is obtained, an analysis is carried out with the isoconversional models of Friedman (FR), Kissinger–Akahira–Sunose (KAS), and Flynn–Wall–Ozawa (FWO) in order to determine the one that best fits the experimental data, and with this, the calculation of the activation energy and the pre-exponential factor is performed. The validation of the model was carried out using the correlation factor, determining that the KAS model is the one that best adjusts for the post-consumer thermoplastic degradation process at the three heating rates. With the use of the kinetic parameters, the variation of the Gibbs free energy is determined in each of the cases, where it is necessary that for structures containing aromatic groups a lower energy is presented, which implies a relative ease of degradation compared to the linear structures.