On the stability of unimolecular films. Part II.-The mechanism of film expansion

Abstract

In Part I it was shown that the adhesion of a unimolecular film of a fatty acid to an underlying aqueous solution could be varied by alteration of the Hydrion concentration of the solution. Increasing the alkalinity effected an increase in the adhesional force of the polar beads, and under isothermal con­ditions a film could be converted from the expanded to the liquid condensed and even to the solid condensed state, by causing an increase in these adhesional forces, this process being perfectly reversible. Whilst ionisation of the acid occurs over a bruited range of P H , the alteration in adhesional forces by a change in P H and the effects of such change on the state of the film extend, contrary to the conclusions of Egner and Hägg,* over a much wider range of P H . Since contraction and expansion of the film coincide with an increase decrease respectively in the adhesional forces holding the polar heads to the surface, we may inter that expansion is effected by a gradual tilting of the molecules from the close packed formation existing in the solid condensed state. We have noted that Müller* from X-ray determinations on crystals of fatty acids suggested that it seemed possible that even in a film in the solid condensed state the molecules were already tilted. Objections to this view were raised by Adam, since he found but one characteristic area for long chain molecules in the solid condensed state, which was, with few exceptions, independent of the nature of the head group. He further found that the area in the liquid condensed state*was dependent on the nature of the head group.