Determination of basic nitrogen content in diesel oil: A miniaturized method by digital image-based colorimetry in a portable device

Abstract

A miniaturized method using a portable device with digital image acquisition and PhotoMetrix PRO app data treatment was developed for the determination of basic nitrogen content in diesel oil. The method was based on the colorimetric titration described in the UOP 269-10 standard protocol. A homemade 3D-printed chamber with controlled light intensity equipped with an USB camera was used for image acquisition after an acid-base titration reaction, carried out in a miniaturized device. After mixing reagents and diesel oil, the images were obtained and converted into RGB (red, green, and blue) histograms, and a partial least squares (PLS) multivariate calibration model was constructed. Parameters of the regression model were evaluated, by the coefficient of determination (R2), the root mean squared error of calibration (RMSEC), the root mean squared error of cross-validation (RMSECV), and the root mean squared error of prediction (RMSEP). Some conditions for the acid-base titration were optimized, such as the concentration of the indicator (68.0 to 272 µmol L-1) and the titrating (HClO4, 0.179 to 1.79 mmol L-1), as well as the volume of diesel oil. With 60 µL of 2.54 mmol L-1 indicator solution, 20 µL of 20 mmol L-1 HClO4 as titrating and using 50 to 1000 µL of diesel oil, optimal conditions were obtained for calibration (RMSEP of 0.377 mg kg-1, RMSECV of 0.307 mg kg-1 with 4 factors). It is important to mention that no differences were observed (p < 0.05) when comparing reference values with the results by the proposed protocol. This proved to be advantageous in relation to the methods described in the UOP 269-10 standard since it was possible to reduce the consumption of reagents and waste generation, in agreement with green analytical chemistry. In addition, this alternative protocol combines simplicity and speed to obtain results with good accuracy, precision and suitable limit of quantification (1 mg kg-1) using a miniaturized system.