Polymer translational diffusion: 2. Non-theta solutions,polystyrene in butan-2-one

The diffusion of linear polystyrene under non-theta conditions in butan-2-one has been studied by Rayleigh light scattered linewidth measurements for the molecular weight range of 2.08 × 10⁶ to 8.7 × 10⁶ and as a function of concentration. By extrapolation of diffusion coefficient values to zero concentration we find that $\text{D}{}_0\text{= 5.5 × 10}{}^{\mathrm{?4}}\text{M}\text{?}{}^{\mathrm{?0.561}}{}_{\mathrm{w}}\text{cm}{}^2\text{s}{}^{\mathrm{?1}}$. The first order concentration dependence $\text{k}{}_{\mathrm{<mtext>d</mtext>}}\text{c}$ changes sign as the molecular weight increases, $\text{k}{}_{\mathrm{<mtext>d</mtext>}}$ being fairly small and negative at low molecular weights and increasingly positive above $\text{M}\text{?}{}_{\mathrm{w}}\text{?230 000}$.