Evidence for a macroscopic electric field in the sedimentation profiles of charged colloids

The determination of molecular masses from barometric sedimentation profiles, a main topic in ultracentrifugal analysis, is thought to be quantitatively correct for non-interacting particles. Whereas this expectation is justified for uncharged colloids or macromolecules at low volume fractions, early ultracentrifugation studies on charged particles had already indicated that the obtained masses might be much too low. More recently, expanded sedimentation profiles have been observed for charged particles, sometimes inflated by orders of magnitude relative to the barometric prediction, which highlights a shortcoming in our understanding of centrifugation of even very dilute charged species. Theory and simulations, anticipated by various authors, now propose that strongly non-barometric sedimentation profiles might be caused by an internal macroscopic electric field that, even for non-interacting particles, significantly decreases the buoyant particle mass. The existence of this field and its intriguing consequences still lack experimental verification. Here we report ultracentrifugation experiments on charged colloidal silica spheres, showing both the existence of such a macroscopic electric field and its drastic effects on the sedimentation profiles of very dilute dispersions at low ionic strength.