Effect of Inorganic Additives on Solutions of Nonionic Surfactants II

The effect of electrolytes and urea on the cloud points of the following three nonionic polyoxyethylated surfactants was studied: cetyl, stearyl, and oleyl alcohol adducts containing 10 ethylene oxide units. The results were similar to those obtained previously with polyethylene oxide and with a polyoxyethylated alkylphenol. Nitrates of cations capable of forming stable solid complexes with model ethers like dioxane raised the cloud points in proportion to their concentrations by up to 35°. They salted the surfactants in through complexation with the ether oxygens. The order of effectiveness in raising the cloud points was lead nitrate > hydrochloric acid > cadmium nitrate > sulfuric acid > magnesium nitrate > aluminum nitrate > nickel nitrate > lithium nitrate > calcium nitrate. Only the nitrates of sodium, potassium, ammonium, and cesium lowered the cloud points, salting the surfactants out. These cations do not form complexes with ether oxygens. Urea, sodium perchlorate, and sodium iodide, which break the structure of water, raised the cloud points. This salting‐in process is ascribed to increased hydration of the ether groups of the polyoxyethylated surfactants due to depolymerization of water by urea and the perchlorate and iodide anions. The bromide, chloride, and sulfate of sodium lowered the cloud points. The surfactant with the alkylaryl moiety was salted in more extensively but salted out only slightly more than the three surfactants with the linear hydrocarbon chain. The data indicate the need for revising the theories of the effects of salts on the solubility of nonelectrolytes in water. None of the theories takes into account the interaction between electrolytes and nonelectrolytes, even though many nonelectrolytes compete with water as ligands for the cations.