An indirect analytical approach based on ATR-FTIR spectroscopy for determining the FFA content in vegetable oils

Abstract

In this study, we developed a novel approach for determining a free fatty acid (FFA) in vegetable oils using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. FFA was converted to carboxylate species by a reaction with phthalimide potassium salt, and the linear relationship between FFA content and ATR-FTIR peak areas at 1541–1616 cm⁻¹ (1595 cm⁻¹ as baseline) was established. Results showed that the R² values obtained during calibration and validation were more than 0.99. The calibration method concurred to within ±0.035% over the range of 0.4% to 4.0% (quantitative determination of the percentage of FFA in oils, expressed as the percentage of oleic acid). In the calibration model, the root mean square error of prediction was 0.0104, the relative error was less than 0.246% and the relative average deviation was 0.386%, respectively. These indexes demonstrated that the calibration model has great accuracy, high precision and good stability. The indirect method established using ATR-FTIR has the advantages of excellent reproducibility, high exactitude, independent of oil type, simple operation and easy cleaning of the instrument surface. The slope of the verification equation between FFA prediction values and American Oil Chemists' Society's (AOCS) titration method was close to 1, R² value was more than 0.99. These indicators suggested that the proposed method and the AOCS method have a good correlation through AOCS titration and ATR–FTIR spectroscopy to determine validation samples parallel. In addition, for comparison, when the AOCS titration and ATR-FTIR spectroscopy methods were used for sample validation, the results indicated that the latter method is more reproducible, highly sensitive and has strong anti-disturbance. Therefore, the ATR-FTIR technique can be applied as a simple, highly sensitive, convenient and timely method for the analysis of FFAs in oils.