Digitalization in Thermodynamics

Digitalization is about data and how they are used. This has always been a key topic in applied thermodynamics. In the present work, the influence of the current wave of digitalization on thermodynamics is analyzed. Thermodynamic modeling and simulation is changing as large amounts of data of different nature and quality become easily available. The power and complexity of thermodynamic models and simulation techniques is rapidly increasing, and new routes become viable to link them to the data. Machine learning opens new perspectives, when it is suitably combined with classical thermodynamic theory. Illustrated by examples, different aspects of digitalization in thermodynamics are discussed: strengths and weaknesses as well as opportunities and threats

Activation volume of selected liquid crystals in the density scaling regime

In this paper, we demonstrate and thoroughly analyze the activation volumetric properties of selected liquid crystals in the nematic and crystalline E phases in comparison with those reported for glass-forming liquids. In the analysis, we have employed and evaluated two entropic models (based on either total or configurational entropies) to describe the longitudinal relaxation times of the liquid crystals in the density scaling regime. In this study, we have also exploited two equations of state: volumetric and activation volumetric ones. As a result, we have established that the activation volumetric properties of the selected liquid crystals are quite opposite to such typical properties of glass-forming materials, i.e., the activation volume decreases and the isothermal bulk modulus increases when a liquid crystal is isothermally compressed. Using the model based on the configurational entropy, we suggest that the increasing pressure dependences of the activation volume in isothermal conditions and the negative curvature of the pressure dependences of isothermal longitudinal relaxation times can be related to the formation of antiparallel doublets in the examined liquid crystals. A similar pressure effect on relaxation dynamics may be also observed for other material groups in case of systems, the molecules of which form some supramolecular structures

Ab initio free energy of vacancy formation and mass-action kinetics in vis-active TiO2

Recent reports have identified bulk defects such as oxygen vacancies as key players in visible-light photoactive TiO2. This would imply greater visible light absorption rates may be possible provided effective defect engineering can be achieved. To further this we have developed methods to simulate vacancy formation in bulk TiO2 using ab initio techniques. Initial results of these methods show an entropic reduction in the free energy of vacancy formation of 2.3 eV over a range of 266 K. The use of this result is illustrated by a 'toy' mass-action kinetics model which offers insight into vacancy concentration, rate constants, and enthalpy of reaction