Electric charging in nonpolar liquids because of nonionizable surfactants

Nonpolar liquids do not easily accommodate electric charges, but it is known that surfactant additives can raise the conductivity and lead to electric charging of immersed solid surfaces. Here, we study the rarely considered conductivity effects induced by surfactant molecules without ionizable groups. Precision conductometry, light scattering, and Karl Fischer titration of sorbitan oleate solutions in hexane reveal a distinctly electrostatic action of the nonionic surfactant. The conductivity in dilute hexane solutions of sorbitan trioleate (Span 85) exhibits two regimes of linear scaling with surfactant concentration and a transition around the critical micelle concentration (cmc). Both regimes can be described with a statistical model of equilibrium charge fluctuations. The behavior observed above the cmc has a direct analogy in systems of ionic surfactants and can be explained by charge disproportionation of reverse micelles. The observed conductivity of Span 85 solutions below the cmc, however, represents a qualitative departure from the behavior reported for ionic surfactants. In the studied surfactant systems, the availability of ionic species may stem from a complexation of the surfactant with ionizable impurities; nonetheless, the ionization process appears to be limited entirely by the surfactant and not by the level of impurity. We therefore propose that nonionizable surfactants can offer a new and robust way of controlling the conductivity in nonpolar liquids.