The K shell absorption jump ratios, jump factors, effective atomic numbers, and electron densities were derived from the measured total mass attenuation coefficient using an energy dispersive X‐ray fluorescence spectrometer for Gd2O3, Gd2(CO3)3H2O, Gd2(C2O4)3H2O, and Gd2(SO4)3 compounds. The total mass attenuation coefficients were measured in the X‐ray energy range from 39.52 to 57.14 keV in a transmission geometry utilizing the Kα2, Kα1, Kβ1, and Kβ2 X‐rays from different secondary source targets excited by the 59.54‐keV photons from an Am‐241 annular source and detected by a Si(Li) detector with a resolution of 160 eV at 5.9 keV. The energy gap, ionization energy, electron affinity, and global electrophilicity parameters of oxide, sulfate, oxalate, and carbonate ions were calculated using density functional theory (B3LYP). The experimental results are discussed based on these parameters. Copyright © 2015 John Wiley & Sons, Ltd.