Thermotics As an Alternative Nonequilibrium Thermodynamic Approach Suitable for Real Thermoanalytical Measurements: A Short Review

Abstract The general concept of temperature is thermodynamically defined in equilibrium somehow predictable even for non-equilibrium; however, it presents some still controversial aspects, as has been shown in a number of studies and reviews that have been published so far. Equilibrium concepts are often extrapolated to apply in micro-localized equilibrium and then appended to non-equilibrium in its entirety, which helps to define out-of-equilibrium temperature on both the macroscopic and microscopic bases. Unfortunately, these theoretical analyses do not provide any guidance on how to assess and understand temperature in practical measurements, such as for conventional thermal analysis. Insufficient use of alternative thermodynamic attitudes is evident especially in the field of thermophysical studies, which do not use static measurements, because they usually involve heating from an external source, i. e., the effect of thermal dynamics on the laboratory sample. This paper presents the applied nonequilibrium thermodynamic concept, historically known as thermotics. This approach takes into account the existence of gradients and heat fluxes, which it assesses from the point of view of the average user, and considers additional influences, going beyond the description of thermodynamics in traditional textbooks. The goal is to extend their validity, even to the state of constant first-time derivatives. At the same time, it points to changes in the temperature due to thermal inertia, which has long been ignored, suggesting that the heat spreads immediately. Moreover, special techniques enabling measurements during its extreme changes probably then require an alternative concept for temperature (tempericity). This opinion paper may provide stimuli for further discussion with regard to the practice of measurements done in the customary nonisothermal mode.