Experimental and Theoretical Insights on the Use of Expired Furosemide as Corrosion Inhibition for Cu in NaCl

Copper and its alloys are extensively employed in a broad range of industrial applications owing to their outstanding mechanical, electrical, and thermal properties. However, their susceptibility to corrosion in aggressive environments remains a major challenge, making corrosion inhibitors one of the most practical and cost-effective strategies for extending their service life. Nevertheless, conventional synthetic inhibitors are often limited by their high cost and adverse environmental and health impacts resulting from their toxicity. In this context, the present work provides a comprehensive experimental and theoretical assessment of the corrosion inhibition performance of Furosemide as an environmentally friendly inhibitor for copper in 3.5 wt.% NaCl solution. The corrosion inhibition performance was evaluated experimentally through gravimetric measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS), while the adsorption behavior of Furosemide was investigated using density functional theory (DFT) calculations. The results demonstrated that expired Furosemide effectively reduced the corrosion rate of copper, with the inhibition efficiency increasing as the inhibitor concentration increased and decreased with increasing temperature. A maximum inhibition efficiency of 90% was achieved at an inhibitor concentration of 400 ppm. The calculated Gibbs free energy of adsorption indicated that Furosemide adsorbs onto the copper surface through a mixed physisorption-chemisorption mechanism, following the Langmuir adsorption isotherm. Potentiodynamic polarization measurements further revealed that Furosemide predominantly suppresses the anodic dissolution reaction, indicating that it behaves as an anodic-type corrosion inhibitor. In addition, the presence of Furosemide significantly decreased the passive current density and shifted the breakdown potential toward more positive values, demonstrating an enhancement in the stability and protective character of the passive film. Electrochemical impedance spectroscopy showed that the corrosion process was governed by diffusion-controlled kinetics in the uninhibited solution, whereas the addition of Furosemide changed the corrosion mechanism to a charge-transfer-controlled process. Density functional theory (DFT) calculations provided additional insight into the inhibition mechanism of Furosemide. The calculated E_HOMO) and E_LUMO values indicate that the molecule can both donate and accept electrons, reflecting its nucleophilic and electrophilic character and its strong affinity for adsorption on the copper surface. Furthermore, the relatively small energy gap (4.631 eV) suggests high molecular reactivity and facilitates electronic interactions with the metal surface. The estimated fraction of electrons transferred further supports the electron-donating ability of Furosemide during the adsorption process. Differences between the Fukui functions and the molecular electrostatic potential (MEP) maps are attributed to the distinct chemical information provided by each descriptor. Whereas the Fukui functions identify the most reactive atomic sites involved in soft donor-acceptor interactions, the MEP maps describe the molecular charge distribution governing electrostatic (hard-hard) interactions.