Molecular Features Of Water Films Created With Bubbles At Hydrophilic And Hydrophobic Surfaces

Considerable attention has been, and is being, given to the physics of water-films associated with bubble interactions at surfaces. In contrast, little information on the chemistry of such films has been reported. This communication reports a method using sum frequency vibrational spectroscopy (SFVS) to describe hydrogen bonding of interfacial water molecules in water films created with bubbles at hydrophilic and hydrophobic surfaces. The SFVS spectra of water films at hydrophilic silica surfaces differ significantly from the spectra of water at a hydrophobic silica surface. The SFVS spectra indicate that a very ordered water structure exists in water films at the hydrophilic silica surface during contact with a bubble and that the extent of hydrogen bonding increases with an increase in contact pressure. Such structural considerations as well as repulsive electrostatic and Van der Waals forces account for film stability for a bubble at the hydrophilic silica surface. In contrast, the SFVS spectra of water at a hydrophobic silica surface show a lack of hydrogen bonding and are characterized by a distinct absorption at about 3700 cm-1 similar to the spectrum of the air/water interface. These results suggest the presence of a water void, or water exclusion zone, at the hydrophobic surface, as supported by X-ray reflectivity measurements reported in the literature, by atomic force microscopy, and by the results from molecular dynamics simulations. Of course the water film at the hydrophobic surface is unstable with film thinning and rupture upon bubble contact. Under these circumstances it is shown that an attractive Van der Waals force between the bubble and the hydrophobic surface can be expected when the water exclusion zone is taken into consideration. As the thickness of the water exclusion zone increases to a thickness corresponding to the size of nano bubbles, the calculated attractive Van der Waals force increases. This analysis may help to explain the so-called ?short range? and ?long range? hydrophobic forces. Keywords: SFVS spectra, hydrophilic silica surface, hydrophobic silica surface