Absence of Specific Cation or Anion Effects at Low Salt Concentrations on the Charge at the Oil/Water Interface

Surfactant-free 2 vol % hexadecane-in-water emulsions have been prepared at pH 9 in the presence of various alkali-metal salts. The surface charge and zeta potential of these emulsions are independent of the identities of the monovalent cations and anions up to 0.01 M electrolyte concentrations. The surface charge density of -5 microC cm(-2) is independent of the identity of the alkali-metal cation among Li, Na, and Cs. The zeta potentials decrease with the log of the salt concentration between 0.1 and 11 mM, independent of the identity of the anion of the sodium salts of iodide, bromide, chloride, fluoride, perchlorate, or iodate or of the identity of the cation of the chloride salts of Li, Na, or Cs. These results imply that neither hydration enthalpies nor ion dispersion potentials are significant in affecting the charge created by the hydroxide ion at the pristine oil/water interface at up to 0.01 M salt concentrations.