Excess molar volumes, speeds of sound and viscosities for binary mixtures of 3-chloroaniline with selected di- and tri-chloro substituted benzene at various temperatures: Comparison with Prigogine–Flory–Patterson theory

Abstract

Excess volume (VE), excess isentropic compressibility (κsE), viscosity deviation (8η) and excess Gibbs energy of activation of viscous flow (G*E) for binary mixtures of 3-chloroaniline (CA) with 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB) and 1,2,4-trichlorobenzene (1,2,4-TCB) at selected compositions are determined from the measured values of densities, speeds of sound, and viscosities of pure components and their mixtures at (T) of 303.15–318.15K, at atmospheric pressure of 0.1MPa. The excess volume (VE), excess isentropic compressibility (κsE), viscosity deviation (8η) and excess Gibbs energy of activation of viscous flow (G*E) have been analyzed in terms of interactions arising due to structural effect, charge–transfer complexes and dipole–dipole interaction between unlike molecules from the experimental data. Excess properties are correlated by the Redlich–Kister equation. The partial molar volumes (V̅m,1, V̅m,2), partial molar isentropic compressibilities (K̅s,m,1, K̅s,m,2), excess partial molar volumes (V̅m,1E and V̅m,2E) and excess partial molar isentropic compressibilities (K̅s,m,1E and K̅s,m,2E) over whole composition range; partial molar volumes (V̅m,1° and V̅m,2°), partial molar isentropic compressibilities (K̅s,m,1° and K̅s,m,2°), excess partial molar volumes (V̅m,1°E and V̅m,2°E) and excess partial molar isentropic compressibilities (K̅s,m,1°E and K̅s,m,2°E) of the components at infinite dilution have also been calculated. The VE results have been analyzed in the light Prigogine–Flory–Patterson theory. An analysis of each of the three contributions viz. interactional, free volume and P* to VE shows that interactional contribution is positive for all binary systems. The free volume effect and P* contribution are negative for all mixtures. The variations of these parameters with composition and temperature have been discussed in terms of intermolecular interactions prevailing in these mixtures.