Many high temperature industrial processes involve gaseous halogen-bearing environments. Essentially, these fall into three subject areas: power generation, waste incineration and especially extractive metallurgy. Fundamental to any understanding of the process chemistry and efficiency in the process technology is an adequate knowledge of background thermodynamics relating to metal-chlorine reactions. In this context, existing free energy/temperature diagrams for metal chlorides do not include many elements, in particular the so called refractory elements from Group V and Group VI of the Periodic Table, namely niobium, tantalum and vanadium, and molybdenum. This paper reports estimation and calculations of the free energy values for these chlorides. The data is discussed in the context of high temperature chlorination processes.