Potential-dependent adsorption and transfer of poly(diallyldialkylammonium) ions at the nitrobenzene|water interface

Electrochemically driven adsorption and partition of a series of poly(diallyldialkylammonium) ions (PDADAA(+): alkyl = methyl, ethyl, propyl, and butyl) at the nitrobenzene (NB)|water (W) interface have been studied using voltammetry and electrocapillary measurements. When the phase-boundary potential, Δφ, that is, the inner potential of the W phase referred to that of the NB phase, is negative, poly(diallyldimethylammonium) (PDADMA(+)) shows little surface activity. The scanning of Δφ in the positive direction induces, first, the adsorption of PDADMA(+) at the interface and, then, the desorption of adsorbed PDADMA(+) ions into the NB phase, followed by the diffusion-limited transfer of PDADMA(+) from W to NB. The elongation of the dialkyl chains gives the stronger surface activity of PDADAA(+) even when Δφ < 0. The PDADAA(+) polyions studied are only slightly more hydrophilic than the corresponding monomers. However, the polycationic character of PDADAA(+) renders the adsorption, desorption, and ion transfer strongly dependent on Δφ and gives rise to unusual, M-shaped electrocapillary curves. The interplay of adsorption-desorption and ion transfer of PDADAA(+) ions induces the electrochemical instability of the interface and the emulsion formation on the NB side of the interface.