The solubility of sodium soaps in dilute aqueous salt solutions has been systematically investigated by direct visual phase behavior observations. The added electrolytes, including simple inorganic salts and bulky organic salts, influence the solubility of sodium soaps in water, as represented by the varied soap Krafft point. Two inorganic salts, sodium chloride and sodium perchlorate, demonstrate a "salting-out" property. On the other hand, tetraalkylammonium bromides show an excellent ability to depress the soap Krafft point and enhance the soap solubility in water. With increasing the tetraalkylammonium ionic size, the degree of "salting-in" of soaps in water increases. However, solubility of pure tetraalkyl ammonium bromide in water decreases as the length of the alkyl chains increases. Furthermore, in the ternary water-tetrapentylammonium bromide(TPeAB)-sodium myristate (NaMy) system, we observed an upper cloud point phenomenon, which greatly shrinks the 1-phase micellar solution region in the phase diagram. This miscibility gap, together with the organic salt solubility limitation, restricts the use of tetraalkylammonium bromides with alkyl chains longer than 4 carbon atoms as effective soap solubility enhancement electrolytes. We also found that for sodium soap with a longer hydrocarbon chain, more tetrabutylammonium salt is required to reduce the soap Krafft point to room temperature. (c) 2005 Elsevier Inc. All rights reserved.