Past exam of the soft condensed matter course of the University of Cambridge / 2018 / Section A / 1 / c

The polymer overlap concentration is reached when there is roughly one chain per coil volume. If $M$ is the chain molar mass, choose the explicit geometric convention $V_{\mathrm{coil}}=4\pi R_g^3/3$, where $R_g$ is the radius of gyration. ThenHere $c^{\ast }$ is mass per solution volume and $N_A$ is the Avogadro constant. A good solvent gives $R_g\propto N^{\nu }$ with $\nu \simeq 0.588$, approximated by $3/5$ in the Flory approximation. With a polystyrene repeat-unit molar mass of about $104.15\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$, the chain has approximately $N=960$ repeat units. This fixes the chain length but not the size amplitude: the problem supplies no statistical segment length or measured coil size.

For a numerical estimate, use the good-solvent size calibration for polystyrene,This empirical calibration is quoted for benzene or toluene near room temperature at molar masses above $2\times 10^5\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$; using it here is a modest extrapolation to $M=10^5\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$. It gives $R_g\simeq 11.3\mathrm{nm}$. ThusThe unrounded calibration gives about $27\mathrm{g}{\mathrm{L}}^{-1}$. This is an estimate under a stated extra material input, not a unique number determined solely by molecular weight and the phrase good solvent. Choosing a different coil-volume convention changes its prefactor. The robust chain-length dependence is $c^{\ast }\propto M^{1-3\nu }\simeq M^{-4/5}$ for a flexible good-solvent coil.