Data for the extraction of chromium(VI) from aqueous sulfate solutions by Alamine 300/Aliquat 336 and di-n-octyl amine/tributyl phosphate (DOA/TBP) have been subjected to formulation of an optimization structure for an effective Cr(VI) separation based on the derivative variation method. Both experimentally and analytically defined optimum Cr(VI) removal efficiencies are ranging about 83-99%, 71-93%, and 60-73% for Alamine 300/Aliquat 336, DOA/TBP, and DOA, respectively. Modeling efforts based on mass-action law methodology and non-homogeneous differential approach have shown considerable success yielding a 10% mean error, and satisfies established limiting behavior of the physical event.