Abstract
AbstractThe method of Flory was used to calculate unperturbed mean‐square dimensions of linear alkanes at 25°C by utilizing the assumption of three‐fold rotational isomerism and allowing, but giving small statistical weight to, configurations involving successive gauche rotations of opposite sign. The necessary 15 × 15 matrix multiplications were made with an IBM 1620 computer. The reciprocal square root of these calculated dimensions were assumed equal to <1/R>Av, and diffusion coefficients of pentane through dotriacontane were then computed by means of the Kirkwood‐Stokes equation. These coefficients were then compared with experimental values from four different solvents and with self‐diffusion measurements. In general, it may be said that theory and experiment agree well for solvents of low viscosity. For more viscous solvents (tetralin and decalin) experimental diffusion coefficients are about 80% larger than those calculated for pentane. As chain length increases, however, better agreement is observed.
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