The orientation of surface-active molecules at interfaces is extremely important in determining the dynamic and equilibrium properties of such systems. Films of fatty acid salts were studied at various pH values of the solutions. It was found that there exists a pH where minimum evaporation of water, maximum foamability, maximum foam stability, minimum contact angle on PMMA surface;maximum single-bubble stability, and maximum surface viscosity are observed. It was also found that this optimum pH value is near the pK(a) of the fatty acid salts. The experimental results are explained in terms of area per molecule, intermolecular spacing, and cooperativity among soap molecules at the interface.! It was further shown that the chain length of the soap molecules can modulate the area per molecule, and hence the intermolecular distance in the film, and thereby influence the ionization behavior of the fatty acid carboxyl group. The pK(a) increases from 6.5 to about 9.0 as the chain length of the fatty acid;salt increases from C-8 to. C-16 Cooperativity among surfactant molecules at the interface is controlled by the area per molecule and intermolecular spacing in the adsorbed film; A small change in intermolecular distance of 0.03 Angstrom can significantly influence various technological processes such as foaming, emulsification, wetting, and retardation of evaporation.