Measurement of Peroxide Values in Oils by Triphenylphosphine/Triphenylphosphine Oxide (TPP/TPPO) Assay Coupled with FTIR‐ATR Spectroscopy: Comparison with Iodometric Titration

Abstract

Hydroperoxides (LOOH) measurement is a common technique to determine the degree of oxidation of oils and fats. Although it appears to have some limitations (time consuming, and uses of toxic solvents as chloroform), the iodometric titration is one of the most common methods. Herein, an alternative method by measuring the oxidation level using Fourier transform infrared (FTIR) with an attenuated total reflectance mode (ATR), based on the stoichiometric conversion of triphenylphosphine (TPP) into triphenylphosphine oxide (TPPO) by hydroperoxides, is proposed. The FTIR‐ATR spectroscopy allows for a simple and accurate detection of the TPPO formed by selective reaction with LOOH, with measurement of its specific adsorption band at 542 cm−1. Calibration is made with TPPO solubilized in butan‐2‐one and covers a range of peroxide values (PV) from ≈2 to ≈800 mEq kg−1. The comparison of the iodometric titration and TPP/TPPO assay is performed with standard hydroperoxides (tert‐butyl hydroperoxide and cumene hydroperoxide). The iodometric titration shows higher PV overestimations in comparison with the TPP/TPPO assay, for both hydroperoxides. An accelerated oxidation of different oils is assessed with the two methods, and the results confirm this observation since higher PV values are measured with the titration method. The TPP/TPPO assay coupled with the ATR‐FTIR spectroscopy appears as a simpler and faster assay, which may limit overestimation and use of toxic solvents, especially suitable for routine analysis of oil and fats. Practical Applications: One of the first indicator of oxidation in oils and fats is the presence of hydroperoxides, therefore, it is important to find a reliable method to assess these oxidation products. One of the most common methods to determine lipid hydroperoxide (LOOH) concentrations is iodometric titration. Although this method is simple to set up, it is labor‐intensive, time consuming, and uses a lot of solvent. TPP/TPPO assay coupled with FTIR‐ATR spectroscopy is a good alternative to the iodometric method since it allows a fast and robust hydroperoxide measurement, with minimal use of organic solvents. This rapid peroxide value determination can be adapted for routine quality control analyses, especially for oxidation in real‐time and accelerated aging assays to evaluate oxidative stability during shelf‐life, for industrial purpose or lab scale experiments. The TPP/TPPO coupled with FTIR‐ATR allows for a fast, simple, reasonably sensitive (adequate for most purposes) and reproducible alternative assay to conventional iodometric titration for peroxide value assessment.

Sesamol can inhibit the formation of glycidyl ester in deep frying palm oil

“…PV represents the content of lipid hydroperoxide, which is the first oxidation product that is released after the free radical reaction progresses in unsaturated fatty acids (Han et al., 2021). Lipid hydroperoxide serves as a precursor to the subsequent formation of the secondary oxidation products aldehydes and ketones (Deyrieux et al., 2018). In Figure 3b, it could be seen that during the 8.0 hr of frying time, the PV reached maximum values of 7.29, 6.30, 5.48, 4.08, and 4.52 mmol/kg at 1.5 hr for PO, PO+0.02%sesamol, PO+0.06%sesamol, PO+0.10%sesamol, and PO+0.02%TBHQ, respectively.…”

NMR Spectroscopy: Determination of Peroxide Value in Vegetable and Krill Oil by Using Triphenylphosphine as Tagging Reagent

“…Iodine can also be formed by oxygen, which liberates iodine from the potassium iodine, and by being absorbed by unsaturated fatty acid bonds. [ 19,37 ] These processes lead to an overestimation of the measuring PV. Another important parameter is the reaction time.…”

Selection of Natural Extracts for their Antioxidant Capacity by Using a Combination of In Vitro Assays

“…In bulk oil system, lipid oxidation was followed by peroxide value (PV) measurement using a FTIR‐ATR spectroscopy (Deyrieux et al, 2018). Unlike most of conventional PV determinations assays, this method does not involve any reagent preparation, nor extraction steps or large volume of organic solvents.…”

“…Experiments were made according to the procedure described by Deyrieux et al (2018). Briefly, a stock solution of TPP in butan‐2‐one (150 mg mL −1 , ~572 mM) was prepared.…”