Exergy and DFT-Based Thermodynamic Analysis of a Rankine–VCR Marine Waste Heat Recovery System

This study investigates the performance of a diesel engine exhaust gas-driven Rankine Cycle-supported vapor compression refrigeration system using quantum chemical approaches beyond conventional thermodynamic analyses. The study focuses on R448A and its components, namely R32, R125, R134a, R1234yf, and R1234ze(E), evaluated at both the system level and the molecular level. At the system level, the Rankine–VCR system was analyzed using a Fortran-based macroscopic thermodynamic model, in which the thermophysical properties of the working fluids were obtained from the NIST Chemistry WebBook. At the molecular level, Density Functional Theory (DFT) calculations were performed to determine molecular structure parameters, including entropy, heat capacity, chemical hardness, and thermal enthalpy correction. The main objective is to investigate the possible relationships between these molecular descriptors and system-level performance indicators, while considering that mass flow rate is primarily governed by cycle thermodynamic properties. The results show that molecular stability and structural order are strongly associated with system performance. Among the R448A components, R32, with the highest chemical hardness (8.19 eV) and lowest molecular entropy (58.9 cal/mol K), exhibits the most favorable exergetic behavior and achieves the highest plant exergy efficiency of 44.92%. In contrast, R1234ze(E), chemically softer (η = 4.42 Ev) and higher in entropy, exhibits the lowest performance. Additionally, R32’s lower thermal enthalpy correction is associated with higher latent heat of vaporization under the selected operating conditions, reducing the required mass flow by approximately 60–70% compared to the other components. This study demonstrates that, in refrigerant selection, not only the global warming potential (GWP) but also quantum parameters such as chemical hardness, molecular entropy, heat capacity, and thermal enthalpy correction can serve as important complementary performance indicators when interpreted together with macroscopic thermodynamic and exergetic results.