We compare new experimental x-ray total mass attenuation coefficients of silicon obtained with the x-ray extended-range technique (XERT) from 5 to 20 keV with theoretical calculations and earlier experimental measurements over a 5 to 50 keV energy range. The accuracy of between 0.27% and 0.5% of the XERT data allows us to probe alternate atomic and solid state wave function calculations and to test dominant scattering mechanisms. Discrepancies between experimental results and theoretical computations of the order of 5% are discussed in detail. No single theoretical computation is currently able to reproduce the experimental results over the entire 5 to 50 keV energy range investigated.