Volcanic gases crucially influence Earth's atmosphere, on long time scales by gradually altering the atmospheric redox state (Gaillard et al., 2011;Kasting, 1993), as well as on short time scales when large amounts are emitted instantaneously during large eruptions (Robock, 2000). Volcanic gas measurements reveal information about Earth's interior, and the chemistry within the cooled and diluted volcanic plume. In that context, the interface between the magmatic gases and the atmosphere and its influence on the gas composition requires consideration. Interpretations of fumarole emissions, particularly those which have considerably cooled at the point of sampling, include a quantitative treatment of gas-rock and gas-fluid interactions. The analysis encompasses both, thermodynamic equilibrium (TE) relationships and the quantification of relative rates of equilibration (see e.g., Giggenbach, 1987Giggenbach, , 1996Henley and Fischer, 2021). In contrast to that, the interaction between magmatic gas and atmospheric air in high-temperature emission processes, for example, at open vents, is difficult to access experimentally and therefore remains poorly studied. Such high-temperature volcanic gases are commonly solely interpreted on the basis of TE relations. While this is likely to be valid for gas bubbles within the magma body, we show that-in contrast to usual assumptions (e.g., Gerlach and Nordlie, 1975;Martin et al., 2006;Moussallam et al., 2019)-TE is not suited to describe magmatic gases at the direct interface between magma and atmospheric air and afterward. TE requires the Gibbs free energy to be minimized prior to macroscopic changes of the system. By modeling the chemical kinetics and turbulent atmospheric mixing in the magma-atmosphere interface, we show that major chemical conversions, cooling, and mixing usually take place on comparable time scales. This leads to complex interactions of these processes ultimately determining the gas composition of the plume within the first fractions of a second after emission into the atmosphere. Then, the gas composition greatly deviates from both, the magmatic gas TE and the TE of the diluted plume and its interpretation requires considering chemical kinetics (i.e., reaction rates) and the dynamics of the system.