Understanding the thermodynamic effects of chemically reactive working fluids in the Stirling heat pump

Within the realm of sustainable heating technologies, this study examines the performance of a Stirling heat pump employing chemically reactive working fluids in contrast to conventional inert counterparts. Reactive working fluids are energy vectors that enable the conversion of not only thermal but also chemical energy within the heat pump. The investigation spans a wide range of theoretical reactive gaseous mixtures, leveraging the ideal gas mixture thermodynamic model. Each fluid is characterized by an equilibrated chemical reaction, denoted as $A_{2\left(g\right)}\rightleftarrows 2A_{\left(g\right)}$, and distinguished by a set of reaction coordinates: the standard entropy change of reaction and standard enthalpy change of reaction. The chemical reaction evolution and thermodynamic properties are observed in each transformation, and the overall coefficient of performance (COP) of the system is evaluated and benchmarked against that of comparable inert working fluids. It is observed that the exothermic reaction during isothermal compression significantly increases the thermal energy supplied to the heat sink, as well as the thermal energy density per unit maximum volume, by up to 269 %, compared to an inert gas system. However, for the majority of reactive fluids studied, chemical reactions introduce irreversibility in the internal regenerator due to heat transfer across a finite temperature difference, contrary to the case of inert working fluids, penalizing the COP. Consequently, a reduction of up to 28 % in the COP is observed. Nevertheless, there exists a range of reactive fluids, characterized by reversible heat exchange in the internal regenerator, offering increased thermal energy transfer to the heat sink without compromising the COP.