The valence states of Mg-Al alloys are compared to those of reference materials (pure Mg and Al metals, and intermetallics). Two methods based on X-ray emission spectroscopy are proposed to determine the phases and their proportion: first, by analyzing the Al valence spectra of the Mg-rich alloys and the Mg valence spectra of the Al-rich alloys; second, by fitting with a linear combination of the reference spectra the Al spectra of the Al-rich alloys and the Mg spectra of the Mg-rich alloys. This enables us to determine that Al and Al3Mg2 are present in the 0–43.9 wt% Al composition range and Mg and Al12Mg17 are present in the 62.5–100 wt% Al composition range. In the 43.9–62.5% Al range, the alloy is single phase and an underestimation of the Al content of the alloy can be estimated from the comparison of the bandwidth of the alloy spectrum to the bandwidths of the reference spectra.
