Effect of Inorganic Additives on Solutions of Nonionic Surfactants V: Emulsion Stability

Abstract

□ Electrolytes often break emulsions to which they were added as active ingredients, adjuvants, or impurities. The stability of oil-in-water emulsions containing octoxynol 9 NF as the emulsifier and various added electrolytes was investigated by measuring droplet size, turbidity, and oil separation on storage at various temperatures and in a centrifugal field at 25°. Electrolytes were added to hexadecane emulsions after emulsification (direct addition); alternatively, hexadecane was emulsified in octoxynol 9–electrolyte mixtures (reverse addition). Xylene emulsions were prepared by direct addition only. Hexadecane emulsions containing 0.10% octoxynol 9 were considerably more stable than xylene emulsions containing 0.60% because the surfactant is practically insoluble in hexadecane, but miscible in all proportions with xylene. An emulsifier soluble in the disperse phase as well as the continuous phase evidently forms less stable interfacial films. The electrolytes investigated were sulfuric and hydrochloric acids, magnesium nitrate, and aluminum nitrate, which salt octoxynol 9 in by complexation between its ether groups and their cations; sodium thiocyanate, which salts the surfactant in by destructuring water; and sodium chloride and sodium sulfate, which salt octoxynol 9 out. The addition of these electrolytes at concentrations up to 2 or 3m to hexadecane emulsions produced fast and extensive creaming, little or no flocculation, no coalescence, and only minor changes in droplet size or turbidity on storage at room temperature. The extent of coalescence during centrifugation was actually reduced by the additives. Such stability is unusual. Droplet size and turbidity depended mainly on octoxynol 9 concentration. The greatest decrease in the former and increase in the latter occurred when the concentration was increased from 0.10 to ~0.4%. All emulsions became slightly coarser on storage at 25°. Stability at 50° was impaired by aluminum nitrate and magnesium nitrate and to a lesser extent by sodium sulfate and sodium chloride. Reverse-addition emulsions differentiated better between the electrolytes than direct-addition emulsions. Electrolytes salting octoxynol 9 in, especially by complexation, generally produced the finest and most stable emulsions. Similarly, xylene emulsions were destabilized more by the electrolytes which salted the emulsifier out than by those salting it in. Centrifugation of hexadecane emulsions at 7800×g compressed the creamed emulsion layer into a plug of clear, transparent, isotropic gel from which coalesced hexadecane separated slowly on further centrifugation. These semisolid gels contained the hexadecane as discrete, uncoalesced droplets because, on immersion in water or octoxynol 9 solutions with or without electrolytes, they turned opaque, liquefied, and redispersed spontaneously into emulsions of nearly the same average droplet size as the original emulsions.