In the past few years the Rietveld method emerged as a routine tool for quantitative phase analysis (QPA) from X-ray diffraction data. Fast and reliable results became possible by combining modern computer technology and optimised mathematical algorithms with the fundamental parameters approach in the Bruker AXS TOPAS software._x000D_
Here the routine analysis of bauxite raw material and of aluminium bath electrolyte is presented. The accuracy of bauxite quantification was tested by analysing the IUCr round robin sample. An agreement of better than one per cent was obtained for minor constituents and a maximum deviation of 2.5 per cent for the major phases. This is excellent agreement with expected results from weighting. Ten different phases were quantified in natural samples from Turkey with a precision better 0.5 per cent for the major phases and one per cent for the minor phases. Additionally, crystallite sizes were obtained from the peak profiles that give valuable information for the processability of the material._x000D_
XRD data from solidified aluminium electrolytes were rapidly measured using silicon strip detector technology. With the LynxEyeTM detector full patterns were collected in 90 seconds and analysed with TOPAS. It is shown how to derive well-established measures such as bath ratio and excess AlF3 from the Rietveld results. These measures are widely used in aluminium production and readily available with very high precision. The excellent agreement with ALCAN reference data demonstrates the outstanding accuracy of the method. The mean deviation between here presented results and reference data is below 0.5 per cent for total CaF2, below 0.25 per cent for excess AlF3 and 0.02 for the bath ratio. The precision of the method was evaluated by repeated measurements.