As the main resource of potash fertilizer, high grade of sylvite (KCl) is mainly separated from halite (NaCl) in soluble potash ores using flotation. An effective flotation collector determines the separation efficiency of sylvite. However, the collector adsorption mechanism is still the subject of much debate due to high ions concentration in the flotation pulp. This paper studies the hydration status of KCl, the flotation behavior of KCl and NaCl with lauric acid and the interfacial water structure of the soluble salts to provide further insights into the fundamental mechanisms at play. The contact angle measurements and laboratory micro-flotation experiments have shown that both the hydration status of KCl and the flotation soluble salts with lauric acid were dependent on the solution composition. Specifically, it was determined that the addition of Na-ions had an adverse effect on the hydrophobicity of KCl crystals. Both KCl and NaCl can be floated with lauric acid. However, flotation of NaCl is greatly enhanced with the addition of K-ions whereas the flotation of KCl is suppressed with the addition of Na-ions. Sum frequency generation (SFG) measurements have found, most strikingly, more disordered water molecules dominating the "structure maker" salt surfaces in a saturated NaCl solution. "Collins Concept" is employed to explain the specific ion binding behaviors in the flotation pulp. (C) 2019 Elsevier Inc. All rights reserved.