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The problem of the dependence of the XRF yield on the irradiation and detection angles and on the sample volume has been critically reviewed. A simple procedure, which accounts for the effect of the sample finite thickness, is given. Applications to the analysis of metal alloys and of organic matrix standards are also reported.

A secondary effect simplified mathematical expression (SESME) was developed to calculate, in a very simple way, the XRF enhancement effect by secondary excitation. This approximate methods makes possible the use of a simple algorithm in the case of a finite thickness sample also. The numerical approximations are quantitatively estimated for samples of infinite thickness and the physical meaning of the formal expression is discussed.