CONDUCTOMETRIC AND CALORIMETRIC STUDIES OF SERIALLY DILUTED AND AGITATED SOLUTIONS: THE DEPENDENCE OF INTENSIVE PARAMETERS ON VOLUME

We systematically analysed the experimental data related to the specific conductivities (χE) and heats of mixing (QEmix) of a series of more than a thousand serially diluted and agitated (SDA) solutions. The results show systematically higher specific conductivities and heats of mixing for SDA solutions with sodium hydroxide than for NaOH with the reference solvents at the same chemical composition. The analysis of the results yielded an extraordinary and unexpected correlation, of an exponential kind, between the two excess parameters and the volume of the solution in the container. In other words, when the specific conductivity of samples of the same preparation that differ in volume (1–200 ml) were measured, the conductivity values were found to increase as the sample volumes decrease. As the influence of volume on the physicochemical properties of the SDA solution was unexpected, the volumes and time of stay at a given volume are not known exactly but are estimates.A new systematic study based on known and constant volumes across the life of the samples is underway. The influence of volume on χE (μS cm−1) and QEmix (J kg−1) turned out to be overwhelming compared with that of time, and is therefore statistically very significant despite the uncertainty in terms of the exact volume value. A simple rationalizing hypothesis is put forth which is consistent with the more general idea of water as a system that is capable of auto-organizing, even in the presence of small perturbations, and is then able to sustain a far from equilibrium state (dissipative structures).