Arachidic acid monolayers at high pH of the aqueous subphase: Studies of counterion bonding

The thermodynamic and morphological properties of arachidic acid monolayers at high pH values (pH 11-13) and temperatures (10 degrees C less than or e qual to T less than or equal to 35 degrees C) are studied. The two-phase co existence region of the surface pressure (Pi)-area (A) isotherms is shifted to higher surface pressures with increasing pH value, just as with increas ing temperature. Accordingly, regularly shaped condensed phase domains are formed which have various textures depending on the pH of the aqueous subph ase. The equation of state, derived recently using the generalized Volmer's equation and the quasichemical equilibrium model of 2D aggregation, was de veloped for the case of dissociating monolayer material taking into account the effects caused by the increase in the number of kinetic entities from the dissociation of ions and a contribution to the surface pressure, relate d to the ion-ion interaction. The experimental Pi-A isotherms can be well d escribed over the entire region of the gaseous and condensed states by the equation of state; The results allow the conclusion that the dissociation o f arachidic acid in the monolayer increases with increasing pH, does not ex ceed 15%, and can be neglected for pH less than or equal to 12. The thermod ynamic characteristics of the aggregation process of arachidic acid in the monolayer, particularly the negative value of standard enthalpy of aggregat e formation and that of standard entropy of aggregation, indicate the forma tion of a highly ordered condensed phase at the expense of the nonordered f luid phase.