Conjugate Acid-Base Interaction Driven Phase Transition at a 2D Air-Water Interface.

A lattice model is described to explain a recent striking Sum Frequency Generation (SFG) observation of a cooperative surface adsorption effect for an organic acid system at an air-water interface. The reported anomalous pH-dependent enhancement in p-methylbenzoic acid (pmBA) arises from an interaction between the acid (HA) and its conjugate base anion (A-), which competes with strong Coulombic repulsion between the conjugate bases (A--A -). Using a statistical mechanical approach, this lattice gas model reveals an analogy to well-studied magnetic systems in which the attraction between the two different molecular species leads to a phase transition to a two-dimensional checkerboard phase consisting of a network of anion-acid complexes formed at the low-dielectric air-water interface. Cooperative acid-anion interactions that control partitioning at solution and aerosol interfaces are of interest to fields ranging from oceanic and atmospheric chemistry, pharmacology, and chemical engineering.