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The paper proposes the identification method of linear and non-linear chromatographic system. Isotherms and lumped mass transfer coefficients of chromatography separating isomer sorbitol and mannitol on D80 adsorbent are determined. The analyses of root mean square error of chromatography elution curves are carried out. The results show that the system studied is non-linear and the theoretical elution curves of the non-linear chromatographic model are more accurate than those of the linear chromatographic model. Results of parameter sensitivity analyses show that elution curves of non-linear chromatographic separation are more sensitive to the variation of parameter “ai” in the adsorption isotherms than to the variation of parameter “bi” as well as lumped mass transfer coefficients.