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A procedure for identification of the compounds in quaternary mixtures has been developed. The proposed procedure is based on the apparent content curves method. From these curves and using the Q parameter, work conditions are selected and quaternary mixtures treated as "pseudoternary" mixtures.A simple strategy to test matrix effects at working wavelengths has been developed, identification limits established and following the identification table quaternary mixtures were easily characterised. The procedure has been applied to the identification of phenols in mixtures by UV-visible spectrophotometry and tocopherols in edible oils by fluorimetry. Results obtained for edible oils are in agreement with the composition obtained by use of the reference method.