Terpene-Based Biofuel Additives (Citral, Limonene, and Linalool) with Chloroform: Experimental and Modeling Study of Volumetric and Transport Properties

In this paper, the thermodynamic properties of terpene mixtures were investigated because they represent a promising group of compounds, usually extracted from biomass, with their most notable application as fuel performance enhancers. The densities, viscosities, refractive indices, and ultrasonic speeds of sound were measured for three binary mixtures, citral + chloroform, limonene + chloroform, and linalool + chloroform, across the full composition range at temperatures between 288.15 K and 323.15 K under atmospheric pressure. Using experimental data, excess molar volumes, viscosity deviations, refractive index deviations, and isentropic compressibility, deviations were calculated. Additionally, properties such as partial molar volumes, excess partial molar volumes, partial molar volumes at infinite dilution, and apparent molar volumes were derived. The excess and deviation properties were analyzed using the Redlich–Kister equation. A single mathematical model, the Heric–Brewer–Jouyban–Acree model, was used to represent densities, viscosities, refractive indices, and ultrasonic speeds of sound. The results obtained in this work suggest that dispersive interactions dominate in the limonene and linalool binary mixtures, while hydrogen bonding plays a significant role in the citral + chloroform system. In summary, dispersive interactions are dominant in nonpolar systems like limonene and linalool, while hydrogen bonding significantly affects the citral-chloroform mixture, where the polar groups in citral interact with chloroform molecules. These differences in intermolecular forces help explain the distinct behavior of each mixture. The modeling outcomes demonstrated that the Heric–Brewer–Jouyban–Acree model accurately correlated the experimental thermodynamic properties, with average percent deviations below 1% for all three systems.