Three recent investigations in the field of thermodynamics of grain boundaries and grain boundary junctions are presented. 1. The grain boundary excess free volume (BFV) along with the surface tension belongs to the major thermodynamic properties of grain boundaries. A special technique, recently developed, makes it possible to measure the BFV for practically any grain boundary and provides a way of estimating the grain boundary excess free volume for grain boundaries of different classes with rather high accuracy. The experimental values of the BFV measured for different grain boundaries are compared and discussed. 2. A new approach will be presented that makes it possible to correctly measure the grain boundary triple line tension. For this the topography at an equilibrated triple junction was measured by atomic force microscopy. Preliminary results of grain boundary triple line energy measurements are presented. 3. The problem is discussed whether it is possible to achieve an equilibrium grain size during grain growth in single phase alloys. Various approaches to the problem are considered. It is shown that the most realistic possibility to stabilize the grain size in a polycrystal is by impurities with negative grain boundary adsorption.