Abstract
The approximate method of calculation of the collisional contribution to transport properties in liquids presented in an earlier paper is now extended to the calculation of the similar contribution to the frictional and diffusion coefficients. For the special case where the diffusing molecule is large compared to its neighbors, the calculated collisional contribution to the frictional coefficient is in good agreement with Stokes' law and the Langevin equation of colloid statistics is valid. However, for small diffusing molecules, the calculated frictional coefficient is not independent of the velocity of the given molecule. Numerical diffusion coefficients using molecular parameters obtained from sonic velocity data are about three times the experimental values as might be expected from the corresponding behavior of the calculated viscosity coefficient contribution previously reported. In spite of the failure of the Stokes equation for the frictional coefficient of small molecules, the Stokes-Einstein equation represents fairly satisfactorily the case of self-diffusion. This is due to the averaging over all velocities of the diffusing molecule.
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