Intermolecular interactions behavior of terpinolene with some halobenzenes: A thermophysical, acoustical, spectral and DFT study

Abstract

Densities, viscosities, speed of sound were experimentally measured for binary mixtures of terpinolene with some halobenzenes such as fluorobenzene, chlorobenzene, bromobenzene at 303.15, 308.15 and 313.15K at atmospheric pressure. Various secondary properties such as molar volume (Vm), excess molar volume (VmE), partial molar volume V−m,io, excess partial molar volume V−m,io,E, apparent molar volume (Vm,Φ,i), deviation in viscosity (Δη), excess Gibbs' free energy of activation of viscous flow (∆G∗E), deviation in speed of sound (Δu), isentropic compressibility (κs), deviation in isentropic compressibility (∆κs), acoustical impedance (z), deviation in acoustical impedances (Δz), intermolecular free length (Lf), partial molar isentropic compression K−s,m,io, excess partial molar isentropic compression K−s,m,io,E and apparent molar isentropic compression (Ks,m,Φ,i) were calculated from the values of primary physical properties. Infinite dilution apparent molar volume (Vm,Φ,1o), infinite dilution apparent molar isentropic compression (Ks,m,Φ,1o), empirical parameters Sv, Bv and Sk, Bk of the Redlich-Rosenberg-Mayer equation with the limiting apparent molar expansibility (EΦo) were also calculated. Some theoretical viscosity of binary mixtures calculating relations like Bingham, Arrhenius, Kendall-Munroe, Grunberg-Nissan (G12), Dolezalek-Schulze (D12), Tamura-Kurata (T12), Katti-Chaudhari (Wvis/RT), and 3-body McAllister (M12, M21) and some theoretical speed of sound calculating relations such as Nomoto relation (unmt), Ideal mixture relation (uimr), Junji relation (ujunji) and Free length theory relation (uflt) were also calculated. FT-IR analysis of binary mixtures at 4:1, 1:1 and 1:4 composition ratios were carried out. The DFT (Density Function Theory) based computational calculations such as bond length, Mulliken charges, theoretical vibrational frequencies, solvation model and NBO calculations were also studied. All the results of excess/deviation properties were fitted with the Redlich-Kister polynomial equation. The results were discussed in term of types, strength and behavior of intermolecular interaction present between components of binary mixtures.