Is interfacial tension of a liquid-air interface thermodynamically a cyclic process?

Abstract

Brønsted (log kB = β pKaHB + C) and Taft (log k = ρ*σ* + log ko) linear free energy equations are applied to the interfacial tension data of N-substituted anilines. The significance of the values of the constants Brønsted β (0.096) and Taft ρ* (0.091) are explained in terms of proton transfer from the acid to the aniline, which is accelerated by electron donating groups. The deprotonation of protonated aniline is accelerated by electron withdrawing groups. Since any thermodynamic property associated with any kind of reaction is a point group, the fact that Brønsted β and Taft ρ* have similar values with opposite sign indicates that the total process taking place at the aniline-air interface is a cyclic one.