A comparative study of diesel analysis by FTIR, FTNIR and FT-Raman spectroscopy using PLS and artificial neural network analysis

• Published in: Analytica chimica acta Vol. 547; no. 2; pp. 188 - 196
• Main Authors: Santos, Vianney O., Oliveira, Flavia C.C., Lima, Daniella G., Petry, Andrea C., Garcia, Edgardo, Suarez, Paulo A.Z., Rubim, Joel C.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 22.08.2005; Elsevier
• Subjects: Analytical chemistry; Artificial neural network; Chemistry; Diesel; Exact sciences and technology; FT-Raman; FTIR; FTNIR; PLS; Spectrometric and optical methods; FTNIR; Diesel; Artificial neural network; FT-Raman; FTIR; PLS; Distillation; Performance evaluation; Viscosity; Fourier transform spectroscopy; Diesel fuel; Calibration; Neural network; Mean square error; Infrared spectrometry; PLS regression; Accuracy; Total attenuated reflection; Sulfur; Comparative study
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2005.05.042

Diesel properties determined by ASTM reference methods as cetane index, density, viscosity, distillation temperatures at 50% (T50) and 85% (T85) recovery, and the total sulfur content (%, w/w) were modeled by FTIR-ATR, FTNIR, and FT-Raman spectroscopy using partial last square regression (PLS) and artificial neural network (ANN) spectral analysis. In the PLS models, 45 diesel samples were used in the training group and the other 45 samples were used in the validation. In the ANN analysis a modular feedforward network was used. Sixty diesel samples were used in the neural network training and other 30 samples were used in the validation. Two different ATR configurations were compared in the FTIR, a conventional (ATR1) and an immersion (ATR2) cell. The ATR1 cell presented the best results, with smaller prediction errors (root mean square error of prediction, RMSEP). The comparison of the three PLS models (FTIR-ATR1, FTNIR, and FT-Raman) shows that reasonable values of R 2 and RMSEP were obtained by the FTIR-ATR1 and FTNIR models in the evaluation of density, viscosity, and T50. The PLS/FT-Raman models presented reasonable results only for the T50 property. None of the techniques was able to generate suitable PLS calibration models for the determination of sulfur content. The ANN/FT-Raman models presented the best performances, with all models presenting R 2-values above 85% some of them with RMSEP values significantly smaller than those obtained with FTIR-ATR and FTNIR. The ANN/FT-Raman and ANN/FTIR-ATR1 models were able to estimate the total sulfur content of diesel with 0.01% (w/w) accuracy.