Self-diffusion coefficients for water and organic solvents at high temperatures along the coexistence curve

The self-diffusion coefficients D for water, benzene, and cyclohexane are determined by using the pulsed-field-gradient spin echo method in high-temperature conditions along the liquid branch of the coexistence curve: 30-350 degrees C (1.0-0.58 g cm(-3)), 30-250 degrees C (0.87-0.56 g cm(-3)), and 30-250 degrees C (0.77-0.48 g cm(-3)) for water, benzene, and cyclohexane, respectively. The temperature and density effects are separated and their origins are discussed by examining the diffusion data over a wide range of thermodynamic states. The temperature dependence of the self-diffusion coefficient for water is larger than that for organic solvents due to the large contribution of the attractive hydrogen-bonding interaction in water. The density dependence is larger for organic solvents than for water. The difference is explained in terms of the van der Waals picture that the structure of nonpolar organic solvents is determined by the packing effect due to the repulsion or exclusion volumes. The dynamic solvation shell scheme [K. Yoshida et al., J. Chem. Phys. 127, 174509 (2007)] is applied for the molecular interpretation of the translational dynamics with the aid of molecular dynamics simulation. In water at high temperatures, the velocity relaxation is not completed before the relaxation of the solvation shell (mobile-shell type) as a result of the breakdown of the hydrogen-bonding network. In contrast, the velocity relaxation of benzene is rather confined within the solvation shell (in-shell type).