Background: Negentropy and entropy fluctuations, which are concepts of out-of-equilibrium thermodynamics, were considered in the development of a simple potentiometric titration method for the study of natural complex systems, in this case humic acids. Results: The method allows, besides the obtainment of traditional titration curves, the observation of response patterns for the out-of-equilibrium evolution throughout the titration pH range, at each point of the titration. Also, two humic acid species distribution models are proposed and interpreted. Conclusions: The obtained potentiometric out-of-equilibrium response patterns (graphical method) are correlated with the negentropic organizational/structural properties of the sample and provide information on its relation with the natural environment.