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A study of electrochemical behaviour of authentic chlordiazepoxide using (DPP) technique which is the famous method using in electrochemical field, which gave atypical sharp very good reduction peak at potential range (-0.94 -1.06) volt versus reference electrode (Ag/AgCl,sat.KCl) . Also we made calibration curve was studied in aqueous solution in the presence of freshly human urine , the relation of the peak current (Ip) versus concentration was linear within the range of [(9.8×10-6)- (74.88×10-6)] molar , with a correlation coefficient of (R= 0.9984). also we made another calibration curve[(7.5×10-6)-(52.6×10-6)] molar , with a correlation coefficient of (R= 0.9974) respectively. (DPP) technique was successfully applied to determine chlordiazepoxide in ten sample of urine and tablets from the famous company using the calibration curve mentioned.The results obtained show a good similarity with concentrations (Taken and Found). Finally we compared our method with slandered method from British pharmacopeia. [ABSTRACT FROM AUTHOR]