We study in detail the barrier distributions extracted from large-angle quasi-elastic scattering of heavy ions at energies near the Coulomb barrier. Using a closed-form expression for scattering from a single barrier, we compare the quasi-elastic barrier distribution with the corresponding test function for fusion. We examine the isocentrifugal approximation in coupled-channels calculations of quasi-elastic scattering and find that for backward angles, it works well, justifying the concept of a barrier distribution for scattering processes. This method offers an interesting tool for investigating unstable nuclei. We illustrate this for the 32 Mg + 208 Pb reaction, where the quadrupole collectivity of the neutron-rich 32 Mg remains to be clarified experimentally.