Thermodynamic calculations are an important tool for prediction of chemical reactions. In many cases the results help to understand and describe the experimental observations. In others, especially if reaction kinetics play a major role, their predictive value can be rather limited and the projected results have to be treated with care. One such case are high temperature chlorine corrosion conditions. For example, thermodynamically a similar corrosion behavior of nickel and molybdenum is predicted in chlorine‐containing atmospheres at low oxygen partial pressures. In contrast to their calculated similarity, experimental results showed much higher resistance of molybdenum against the chlorinating attack. Above 800 °C nickel is rapidly consumed, whereas molybdenum remains almost inert. This paper reviews the literature on the corrosion mechanisms and kinetics of nickel and molybdenum in chlorine‐containing environments as well as in mixed oxygen‐chlorine‐containing atmospheres. Based on the literature review, differences in their reaction kinetics are discussed, taking into account the deviation from an ideal thermodynamic correlation between the partial pressure and the reaction kinetics via the often used Hertz‐Langmuir equation. Finally it is shown that the findings concerning the special characteristics of molybdenum and nickel and the conclusions drawn from experimental observations on high temperature chlorine corrosion can also be transferred to other metals.

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Operating atmospheres of many industrial high temperature processes contain a certain amount of halogens, in most cases chlorine. Halogens have the tendency of forming volatile metal chlorides of the general formula MxCly, which are well known to play a critical role in high temperature corrosion processes, when present at a significant amount. Thermodynamic calculations give a valuable hint, whether a reaction product can occur and how volatile such products can potentially be, when the partial pressures are calculated. However, such calculations reflect thermodynamically stable conditions, while in open systems the local kinetics control the process of surface reactions. For each specific condition, the reaction rates and thus the corrosion rates have to be determined. In previous work, we have shown that corrosion kinetics which lead to the formation of volatile products follows different steps. In this work, a mathematical model is developed in which the different steps, which are required for the formation of metal chlorides and their removal from the surface are described. It is assumed that the slowest of such formation or transport steps determines the kinetics of high temperature corrosion. The application of this model on the literature data shows that by this model it becomes possible to identify the slowest and therefore rate determining step.

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