Partial Least Squares, Experimental Design, and Near-Infrared Spectrophotometry for the Remote Quantification of...

Near-infrared spectrophotometry and partial least squares regression (PLSR) were evaluated to create a pleasantly simple yet effective approach for measuring HNO₃ concentration with varying temperature levels. A training set, which covered HNO₃ concentrations (0.1-8 M) and temperature (10-40 °C), was selected using a D-optimal design to minimize the number of samples required in the calibration set for PLSR analysis. The top D-optimal-selected PLSR models had root mean squared error of prediction values of 1.4% for HNO₃ and 4.0% for temperature. The PLSR models built from spectra collected on static samples were validated against flow tests including HNO₃ concentration and temperature gradients to test abnormal conditions (e.g., bubbles) and the model performance between sample points in the factor space. Based on cross-validation and prediction modeling statistics, the designed near-infrared absorption approach can provide remote, quantitative analysis of HNO₃ concentration and temperature for production-oriented applications in facilities where laser safety challenges would inhibit the implementation of other optical techniques (e.g., Raman spectroscopy) and in which space, time, and/or resources are constrained. The experimental design approach effectively minimized the number of samples in the training set and maintained or improved PLSR model performance, which makes the described chemometric approach more amenable to nuclear field applications.