Three-dimensional voltammetry: Use of chronoamperometric E-t-i data to achieve second-order advantage.

This work studied the use of three-dimensional voltammetry, particularly potential-time-current (E-t-i) data, on the development of electroanalytical methods. E-t-i data was obtained by taking chronoamperograms at potentials applied as pulses on a staircase waveform. By using this three-way kind of data and appropriate calibration algorithms, the possibility of achieving the second-order advantage was evaluated in the determination of ferrocyanide in the presence of the uncalibrated interference hydroquinone as a model system. The determination of acetaminophen in urine samples, where ascorbic acid and uric acid play the major roles as interferents was also studied. Parallel factor analysis (PARAFAC) and multivariate curve resolution alternating least-squares (MCR-ALS) were the algorithms employed in this work. Both algorithms successfully achieved the second-order advantage by correctly predicting the concentrations of the validation synthetic samples. Excellent predictions were obtained in the direct analysis of acetaminophen-spiked urine samples by E-t-i data and MCR-ALS.