It is stated that, for a given element A to be determined, fluorescent intensity I A is dependent as much on the concentration of A as on the absorption characteristics of the unknown sample in regard to both the emergent fluorescent radiation and the generally complex incident exciting radiation. It is also shown that if the primary radiation can be assumed to be equivalent to a constant monochromatic radiation a number of methods, especially dilution or multidilution procedures, can be devised for eliminating the influence of absorption differences between unknown and standard specimens. The theory of “corrected” fluorescent intensities free from matrix effects is put forward. The influence of the usually polychromatic or composite structure of the incident beam is thoroughly investigated, both theoretically and experimentally, and it is demonstrated that matrix effects are completely compensated in all cases, using the dilution methods, whatever the particular structure of the incident beam. So, for the purpose of quantitative analysis, the concentrations calculated from the corrected intensities are in principle exact values, within a 0.1–0.2% relative accuracy. Practical consequences are considerable. Using homogeneous specimens, the method compensates exactly for absorption and enhancement effects and its practical accuracy ranges from a few tenths of one percent to a few percent, relative, according to the more or less favourable measurement conditions encountered. High sensitivity can be retained if necessary. The method is quasi absolute, as only a few standard specimens are used, made up either of pure compounds or of a well known reference sample. No calibration curves are needed and calculations are remarkably simple. All elements relevant to X-ray fluorescence can be determined in every kind of material (ores, rocks, chemicals, metals and alloys, ⋯) using either ordinary solutions or solid solutions as obtained by fusion techniques.
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