A reaction-based process has been developed for the selective removal of carbon dioxide (CO2) from a multicomponent gas mixture to provide a gaseous stream depleted in CO2 compared to the inlet CO2 concentration in the stream. The proposed process effects the separation of CO2 from a mixture of gases (such as flue gas/fuel gas) by its reaction with metal oxides (such as calcium oxide). The Calcium based Reaction Separation for CO2 (CaRS—CO2) process consists of contacting a CO2 laden gas with calcium oxide (CaO) in a reactor such that CaO captures the CO2 by the formation of calcium carbonate (CaCOa). Once “spent”, CaCO3 is regenerated by its calcination leading to the formation of fresh CaO sorbent and the evolution of a concentrated stream of CO2. The “regenerated” CaO is then recycled for the further capture of more CO2. This carbonation-calcination cycle forms the basis of the CaRS—CO2 process. This process also identifies the application of a mesoporous CaCO3 structure, developed by a process detailed elsewhere, that attains >90% conversion over multiple carbonation and calcination cycles. Lastly, thermal regeneration (calcination) under vacuum provided a better sorbent structure that maintained reproducible reactivity levels over multiple cycles.