The spaceborne detection of volcanic ash clouds at infrared wavelengths helps to avoid regions with enhanced volcanic ash concentrations that pose a threat to aviation. Current volcanic ash data retrievals require detailed information on microphysical properties and the refractive index of volcanic ash, which are highly variable. Uncertainties in the latter currently limit the quality of volcanic ash nowcasts. Here, we introduce a novel method to calculate the complex refractive indices of volcanic ashes at wavelengths from 5 to 15 μm from measurements of their individual components based on generic petrological ash compositions. Thereby the refractive indices for volcanic glasses and bulk volcanic ashes of different chemical compositions are derived. The variability of the latter is mainly influenced by the silica content and the porosity and to a minor degree by the glass-to-crystals ratio. Calculating optical properties exhibits an equally large impact of bulk composition and grain size distribution, whereas particle shape is considered less important for particle sizes of the order 1 μm. Using these optical properties to determine brightness temperature differences between the 11 μm and 12 μm channels we show that the effect of ash composition is non-negligible for modern satellite instruments. Particularly, the dependence of the volcanic ash on the silica content (and to a much smaller extent on the glass-to-crystals ratio) is observable in its refractive index, its optical properties and the brightness temperature difference, indicating that composition might be retrievable to some degree by remote sensing methods.