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Electropherograms of serum albumin with BPE under physiological conditions in vitro are determined using external calibration Hummel-Dreyer (HD) method by capillary electrophoresis. To obtain the interaction parameters, the experimental data were analyzed by three functional forms: Nonlinear equation, Scatchard equation and Klotz equation. ResultsThree form functions were fitted with the interaction parameters. As a simple and effective method, external calibration HD method could be used to analyze the protein pollutant interaction in the food safety field.