Temperature Programmed Carbonation developed using a temperature programmed fixed bed unit. Sorbents are kept in contact with a gas stream containing a 10% CO2 mole fraction, and are subjected to a 5 C/min temperature ramp. Calcium carbonate, lithium orthosilicate and a novel lithium orthosilicate modified sorbent are considered for these runs. TPC-TPDC runs confirm thermodynamic predictions for thermal inversion points. Furthermore, TPD-TPDC runs show that the novel lithium orthosilicate based sorbent provides a very stable and increased CO2 sorption capacity over 10 absorption-regeneration cycles, while calcium carbonatetemperature programmed fixed bed unit. We develop TPC-TPDC runs using calcium carbonate and lithium orthosilicate. We are able to predict sorbent regeneration and temperature inversion points.