A fourier transform infrared spectroscopic method for determining butylated hydroxytoluene in palm olein and palm oil

A simple, rapid, and direct FTIR spectroscopic method was developed for the determination of BHT content in refined, bleached, and deodorized (RBD) palm olein and RBD palm oil. The method used sodium chloride windows with a 50-mm transmission path. Fifty stripped oil samples of both RBD palm olein and RBD palm oil were spiked with known amounts of BHT concentrations up to 300 mg/kg (ppm). The data were separated into two sets for calibration and validation using partial least squares models. FTIR results for both oils correlated well with results obtained by the IUPAC HPLC-based method. For RBD palm olein, the coefficient of determination (R ²) was 0.9907 and the SE of calibration (SEC) was 8.47 ppm. For RBD palm oil, an R ² of 0.9848 and an SEC of 10.73 ppm were achieved. Because of the significant decrease in analysis time and reduction in solvent usage, this FTIR method for BHT is especially well suited for routine quality control applications in the palm oil industry.     

Rapid method for determining moisture content in crude palm oil by Fourier transform infrared spectroscopy

A simple, rapid, and direct Fourier transform infrared (FTIR) spectroscopic method was developed for the determination of moisture content of crude palm oil (CPO). The calibration set was prepared by adding double-distilled water to dried CPO in ratios (w/w) between 0 and 13% moisture. A partial least squares (PLS) regression technique was employed to construct a calibration model followed by cross-validation step. The accuracy of this method was comparable to the accuracy of the American Oil Chemists' Society's vacuum oven method, which is used for determination of moisture and volatile matter, with mean difference (MD_a) of 0.0105, a coefficient of determination (R ²) and a standard error of calibration (SEC) of 0.9781 and 0.91, respectively. It is also comparable to the accuracy of the International Union of Pure and Applied Chemistry's distillation method with MD_a, R ², and SEC of 0.0695, 0.9701, and 0.65, respectively. The study showed that midband FTIR spectroscopy combined with the PLS regression calibration technique is rapid and accurate for determination of moisture content of CPO samples with a total analysis time of less than 2 min and less than 2 mL of sample.     

Determination of iodine value of palm oil by fourier transform infrared spectroscopy

A rapid method for the quantitative determination of iodine value (IV) of palm oil products by FTIR transmission spectroscopy is described. A calibration standard was developed by blending palm stearin and superolein in specific ratios that covered a range of 27.9 to 65.3 IV units. The spectra of these standards was measured in the range between 3050 and 2984 cm⁻¹, corresponding to the absorption band of=C-H cis stretching vibration. A partial least squares calibration model for the prediction of IV was developed to quantify the IV of palm oil products. A validation approach was used to optimize the calibration with a correlation coefficient of R ²=0.9995 and a standard error of prediction of 0.151. This study concludes that the FTIR transmission approach can be used to determine the IV of palm oil products with a total analysis time per sample of less than 2 min for liquid samples.     

A new method for determining gossypol in cottonseed oil by FTIR spectroscopy

A new method was developed to determine the gossypol content in cottonseed oil using FTIR spectroscopy with a NaCl transmission cell. The wavelengths used were selected by spiking clean cottonseed oil to gossypol concentrations of 0–5% and noting the regions of maximal absorbance. Transmittance values from the wavelength regions 3600–2520 and 1900–800 cm⁻¹ and a partial least squares (PLS) method were used to derive FTIR spectroscopic calibration models for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils. The coefficients of determination (R ²) for the models were computed by comparing the results from the FTIR spectroscopy against those obtained by AOCS method Ba 8-78. The R ² were 0.9511, 0.9116, and 0.9363 for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils, respectively. The SE of calibration were 0.042, 0.009, and 0.060, respectively. The calibration models were cross-validated within the same set of oil samples. The SD of the difference for repeatability and accuracy of the FTIR method were better than those for the chemical method. With its speed (ca. 2 min) and ease of data manipulation, FTIR spectroscopy is a useful alternative to standard wet chemical methods for rapid and routine determination of gossypol in process and/or quality control for cottonseed oil.     

Determination of olive oil free fatty acid by fourier transform infrared spectroscopy

A new procedure for determining free fatty acids (FFA) in olive oil based on spectroscopic Fourier transform infrared-attenuated total reflectance spectroscopy measurements is proposed. The range of FFA contents of samples was extended by adding oleic acid to several virgin and pure olive oils, from 0.1 to 2.1%. Calibration models were constructed using partial least-squares regression (PLSR). Two wavenumber ranges (1775–1689 cm⁻¹ and 1480–1050 cm⁻¹) and several pretreatments [first and second derivative; standard normal variate (SNV)] were tested. To obtain good results, splitting of the calibration range into two concentration intervals (0.1 to 0.5% and 0.5 to 2.1%) was needed. The use of SNV as a pretreatment allows one to analyze samples of different origins. The best results were those obtained in the 1775–1689 cm⁻¹ range, using 3 PLSR components. In both concentration ranges, at a confidence interval of α = 0.05, no significant differences between the reference values and the calculated values were observed. Reliability of the calibration vs. stressed oil samples was tested, obtaining satisfactory results. The developed method was rapid, with a total analysis time of 5 min; it is environment-friendly, and it is applicable to samples of different categories (extra virgin, virgin, pure, and pomace oil).     

Quantitative analysis of palm carotene using fourier transform infrared and near infrared spectroscopy

β-Carotene content is usually determined by using ultraviolet (UV)-visible spectrophotometry at 446 nm. In this study, two spectroscopic techniques, namely, Fourier transform infrared (FTIR) and near infrared (NIR) spectroscopy, have been investigated and compared to UV-visible spectrophotometry to measure the β-carotene content of crude palm oil (CPO). Calibration curves ranging from 200 to 800 ppm were prepared by extracting β-carotene from original CPO using open-column chromatography. Separate partial least squares calibration models were developed for predicting β-carotene based on the spectral region from 976 to 926 cm⁻¹ for FTIR spectroscopy and 546 to 819 nm for NIR spectroscopy. The correlation coefficient (R ²) and standard error of calibration obtained were 0.972 and 25.2 for FTIR and 0.952 and 23.6 for NIR techniques, respectively. The validation set gave R ² of 0.951 with standard error of performance (SEP) of 25.78 for FTIR technique and R ² of 0.979 with SEP of 19.96 for NIR technique. The overall reproducibility and accuracy did not give comparable results to that of spectrophotometric method; however, the standard deviation of prediction was still within ±5% β-carotene content over the range tested. Because of their rapidness and simplicity, both FTIR and NIR techniques provide alternative means of measuring β-carotene content in CPO. In addition, these two spectroscopic techniques are environmentally friendly since no solvent is involved.     

Multivariate calibration of fourier transform infrared spectra for determining thiobarbituric acid-reactive substance content in palm oil

Fourier transform infrared (FTIR) spectra of palm oil samples between 2900 and 2800 cm⁻¹ and 1800 and 1600 cm⁻¹ were used to compare different multivariate calibration techniques for quantitative determination of their thiobarbituric acid-reactive substance (TBARS) content. Fifty spectra (in duplicate) of palm oil with TBARS values between 0 and 0.25 were used to calibrate models based on partial least squares (PLS) and principal components regression (PCR) analyses with different baselines. The methods were compared for the number of factors, coefficients of determination (R ²), and accuracy of estimation. The standard errors of prediction (SEP) were calculated to compare their predictive ability. The calibrated models generated three to eight factors, R ² of 0.9414 to 0.9803, standard error of estimation (SEE) of 0.0063 to 0.0680, and SEP of 1.20 to 6.67.     

Detailed mapping of biaxial orientation in polyethylene terephthalate bottles using polarised attenuated total reflection FTIR spectroscopy

Polarised attenuated total reflection FTIR spectroscopy has been used for detailed orientation mapping of 2l polyethylene terephthalate bottles subjected to different preform heating times. The results for the bottle with the standard preform heating time reveal significant surface orientation variations along the bottle hoop and length directions, with the inner bottle surface also showing consistently greater chain orientation in the hoop direction than found for the outer surface. Decreasing the preform heating time has less effect on the chain orientation than increasing the heating time, with the latter causing reduced chain orientation in the final bottle. The absorbance of the 1340 cm⁻¹ band provides a quick and reliable indication of these chain orientation trends. In contrast, the extent of benzene ring orientation parallel to the bottle surface showed little variation and remained consistently high at the majority of the surface bottle positions probed.     

Diffuse reflectance fourier transform infrared spectroscopy of triacylglycerol and oleic acid adsorption on synthetic magnesium silicate

Diffuse reflectance fourier transform infrared (FTIR) was used to observe adsorption complexes of triacylglycerol and oleic acid on silica gel and synthetic magnesium silicate. The spectra provide evidence of the nature of the surface interaction. Triacylglycerol was shown to be physically adsorbed to both adsorbents. Oleic acid was physically adsorbed to the silica gel, but both physically and chemically adsorbed to the magnesium silicate. The FTIR spectrum of magnesium silicate that was used to treat a degraded frying oil was similar to that of oleic acid adsorbed on magnesium silicate.     

Rapid and direct lodine value and saponification number determination of fats and oils by attenuated total reflectance/fourier transform infrared spectroscopy

A simple, rapid and reproducible method of determining the iodine value (IV) and saponification number (SN) for fats and oils was developed with an attenuated total reflectance/Fourier transform infrared spectrometer and commercially available triglycerides as calibration standards. Partial least squares was used to determine the spectral regions correlating with the known chemical IV and SN values, and the calibration set was augmented with additional standards generated by spectral co-adding techniques. The calibration model obtained was used to analyze commercially available fats and oils with a wide range of IV and SN values, and the results were compared to the values obtained by American Oil Chemists’ Society methods. With the spectrometer calibrated and programmed, IV and SN results could be obtained within 2–3 min per sample, a major improvement over conventional wet chemical methods.     

Simultaneous determination of lodine value and trans content of fats and oils by single-bounce horizontal attenuated total reflectance fourier transform infrared spectroscopy

A method for the simultaneous determination of iodine value (IV) and trans content from the Fourier transform infrared (FTIR) spectra of neat fats and oils recorded with the use of a heated single-bounce horizontal attenuated total reflectance (SB-HATR) sampling accessory was developed. Partial least squares (PLS) regression was employed for the development of the calibration models, and a set of nine pure triacylglycerols served as the calibration standards. Regression of the FTIR/PLS-predicted IV and trans contents for ten partially hydrogenated oil samples against reference values obtained by gas chromatography yielded slopes close to unity and SD of <1. Good agreement (SD<0.35) also was obtained between the trans predictions from the PLS calibration model and trans determinations performed by the recently adopted AOCS FTIR/SBHART method for the determination of isolated trans isomers in fats and oils.     

Characterization of edible oils,butters and margarines by Fourier transform infrared spectroscopy with attenuated total reflectance

The combination of attenuated total reflectance (ATR) and mid-infrared spectroscopy (MIRS) with statistical multidimensional techniques made it possible to extract relevant information from MIR spectra of lipid-rich food products. Wavenumber assignments for typical functional groups in fatty acids were made for standard fatty acids: Absorption bands around 1745 cm⁻¹, 2853 cm⁻¹, 2954 cm⁻¹, 3005 cm⁻¹, 966 cm⁻¹, 3450 cm⁻¹ and 1640 cm⁻¹ are due to absorption of the carbonyl group, C−H stretch, =CH double bonds of lipids and O−H of lipids, respectively. In lipid-rich food products, some bands are modified. Water strongly absorbs in the region of 3600–3000 cm⁻¹ and at 1650 cm⁻¹ in butters and margarines, allowing one to rapidly differentiate the foods as function of their water content. Principal component analysis was used to emphasize the differences between spectra and to rapidly classify 27 commercial samples of oils, butters and margarines. As the MIR spectra contain information about carbonyl groups and double bonds, the foods were classified with ATR-MIR, in agreement with their degree of esterification and their degree of unsaturation as determined from gas-liquid chromatography analysis. However, it was difficult to differentiate the studied food products in terms of their average chainlength.     

Upgrading the AOCS infrared trans method for analysis of neat fats and oils by fourier transform infrared spectroscopy

An automated protocol for the direct, rapid determination of isolated trans content of neat fats and oils by Fourier transform infrared (FTIR) spectroscopy was devised, based on a simple modification of the standard AOCS trans method, eliminating the use of CS₂ and methylation of low trans samples. Through the use of a commercially available, heated transmission flow cell, designed specifically for the analysis of neat fats and oils, a calibration (0–50%) was devised with trielaidin spiked into a certified, trans-free soybean oil. The single-beam spectra of the calibration standards were ratioed against the single-beam spectrum of the base oil, eliminating the spectral interference caused by underlying triglyceride absorptions, facilitating direct peak height measurements as per the AOCS IR trans method. The spectrometer was preprogrammed in Visual Basic to carry out all spectral manipulations, measurements, and calculations to produce trans results directly as well as to provide the operator with a simple interface to work from. The derived calibration was incorporated into the software package, obviating the need for further calibration because the program includes an automatic recalibration/standardization routine that automatically compensates for differences in optical characteristics between instruments, instrument drift over time, and cell wear. The modified AOCS FTIR analytical package was evaluated with Smalley check samples for repeatability, reproducibility, and accuracy, producing SD of ± 0.07, 0.13, and 0.70 trans, respectively, the FTIR predictions being linearly related to the Smalley means (r=0.999; SD=± 0.46), and well within one SD of the Smalley sample means. Calibration transfer was assessed by implementing the calibration on a second instrument and reanalyzing the Smalley check samples in cells of two different pathlengths (25- and 50-μm). There were no statistically significant differences between the FTIR trans predictions obtained for the Smalley samples from the two instruments and two cells, indicating that the software was able to adjust the calibrations to compensate for differences in instrument response and cell pathlength. The FTIR isolated trans analysis protocol developed by the McGill IR Group has the benefit of being based on the principles of an AOCS-approved method, matches its accuracy, and allows the analysis to be performed on both neat fats and oils, producing trans predictions in less than 2 min per sample. It is suggested that this integrated approach to trans analysis, which requires a minimum level of sample manipulation and operator skill, be considered as a modification of the proposed Recommended Practice CD14b-95.     

Determination of hexane residues in vegetable oils with FTIR spectroscopy

The FTIR spectroscopy method was developed for the determination of hexane residues in palm and groundnut (peanut) oils. The method was based on horizontal attenuated total reflectance with a ZnSe crystal at 45° at room temperature, and partial least squares (PLS) statistics were used to derive calibration models. The accuracy of the method was comparable to that of the AOCS Method Ca 3b-87, with coefficients of determination (R ²) of 0.9866 and 0.9810 for palm and groundnut oils, respectively, and SE of calibration of 3.83 and 4.91, respectively. The calibration models were validated, and the R ² of validation and the SE of prediction computed. The SD of the difference for repeatability for the method was comparable to that for the standard AOCS method when used for palm and groundnut oils. With its speed and ease of data manipulation by computer software, FTIR spectroscopy has an advantage over present chemical methods, which require preparation of the oil using toxic solvents before GC.     

Trans fatty acid determination in fats and margarine by fourier transform infrared spectroscopy using a disposable infrared card

The use of a disposable polyethylene infrared (IR) card as a sample carrier for the quantitative determination of trans content of fats and oils and margarine by Fourier transform IR spectroscopy was investigated. Standards prepared by dissolving trielaidin in a zero-trans oil were used to develop partial least squares (PLS) calibrations for both the IR card and a 100-μm transmission flow cell. These calibrations were then used to predict a series of gas chromatographically-preanalyzed unknowns, the trans predictions obtained using the card being comparable to those obtained with the transmission flow cell. Somewhat improved performance could be obtained when the spectral data from the card were normalized to compensate for inherent variations in path length and variability in sample loading. Both IR methods tracked the gas chromatographic reference trans values very well. A series of margarine samples was also analyzed by the card method, producing results similar to those obtained using a flow cell. For the analysis of margarines, the card method has the advantage that the trans analysis can be performed directly on microwave melted emulsions because moisture is not retained on the card. Overall, the disposable IR card was shown to work well and has the benefit of allowing trans analyses to be carried out without requiring investment in a heated flow cell or attenuated total reflectance accessory.     

Inline monitoring of styrene/butyl acrylate miniemulsion polymerization with attenuated total reflectance/Fourier transform infrared spectroscopy

The copolymerization of styrene/butyl acrylate in a miniemulsion was monitored inline with an attenuated total reflectance/Fourier transform infrared (ATR–FTIR) probe. ATR–FTIR spectroscopy was used to track the concentration of the monomers, thereby providing conversion and polymer composition data. Offline gravimetry and ¹H‐NMR spectroscopy were used to provide a comparison with the ATR–FTIR data. Because of inconsistent results with a univariate method, a multivariate or partial least squares calibration method using the full spectra of the reactions was selected and gave excellent results. No statistically significant differences were found between the offline and ATR–FTIR spectroscopy data coupled with multivariate statistics, and this confirmed that ATR–FTIR spectroscopy is a reliable tool for monitoring the conversion and polymer composition in miniemulsion polymerizations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 46–52, 2007     

Quantitative determination of hydroperoxides by fourier transform infrared spectroscopy with a disposable infrared card

Disposable polyethylene infrared cards (3M IR cards) were investigated for their suitability for the quantitative determination of peroxide value (PV) in edible oils relative to a conventional transmission flow cell. The analysis is based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Preliminary work indicated that the cards, although relatively consistent in their pathlength (±1%), had an overall effective pathlength variation of ±∼5%, caused by variability in loading of the oil onto the cards. This loading variability was reduced to <0.5% by developing a normalization protocol that is based on the peak height of the ester linkage carbonyl overtone band at 3475 cm⁻¹, which allowed one to obtain consistent and reproducible spectra. The standard PV calibration approach, based on the TPPO peak height at 542 cm⁻¹, failed because of unanticipated card fringing in the region where the measurements were being made. However, the development of a partial-least-squares (PLS) calibration provided a means of eliminating the interfering effect of the fringes and allowed the TPPO band to be measured accurately. An alternate approach to the standardized addition of TPP reagent to the oil was also investigated by impregnating the 3M IR cards with TPP, thus allowing the reaction to take place in situ. The spectral analysis protocols developed (normalization/calibration) were programmed to automate the PV analysis completely. The 3M card-based Fourier transform infrared PV methods developed were validated by analyzing oxidized oils and comparing the PV predictions obtained to those obtained in a 100-μm KCI flow cell. Both card methods performed well in their ability to predict PV. The TPP-impregnated 3M card method reproduced the flow cell PV data to within ±1.12 PV, whereas the method with an unimpregnated card was accurate to ±0.92 PV over the calibrated range (0–25 PV). Our results indicate that, with spectral normalization and the use of a PLS calibration, quantitative PV data, comparable to those obtained with a flow cell, can be provided by the 3M IR card. With the analytical protocol preprogrammed, the disposable 3M card provides a simple, rapid and convenient means of carrying out PV analyses, suitable for quality control laboratories, taking about 2–3 min per analysis.     

Quantitative determination of hydroperoxides by fourier transform infrared spectroscopy with a disposable infrared card

Disposable polyethylene infrared cards (3M IR cards) were investigated for their suitability for the quantitative determination of peroxide value (PV) in edible oils relative to a conventional transmission flow cell. The analysis is based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Preliminary work indicated that the cards, although relatively consistent in their pathlength (±1%), had an overall effective pathlength variation of ±∼5%, caused by variability in loading of the oil onto the cards. This loading variability was reduced to <0.5% by developing a normalization protocol that is based on the peak height of the ester linkage carbonyl overtone band at 3475 cm⁻¹, which allowed one to obtain consistent and reproducible spectra. The standard PV calibration approach, based on the TPPO peak height at 542 cm⁻¹, failed because of unanticipated card fringing in the region where the measurements were being made. However, the development of a partial-least-squares (PLS) calibration provided a means of eliminating the interfering effect of the fringes and allowed the TPPO band to be measured accurately. An alternate approach to the standardized addition of TPP reagent to the oil was also investigated by impregnating the 3M IR cards with TPP, thus allowing the reaction to take place in situ. The spectral analysis protocols developed (normalization/calibration) were programmed to automate the PV analysis completely. The 3M card-based Fourier transform infrared PV methods developed were validated by analyzing oxidized oils and comparing the PV predictions obtained to those obtained in a 100-μm KCI flow cell. Both card methods performed well in their ability to predict PV. The TPP-impregnated 3M card method reproduced the flow cell PV data to within ±1.12 PV, whereas the method with an unimpregnated card was accurate to ±0.92 PV over the calibrated range (0–25 PV). Our results indicate that, with spectral normalization and the use of a PLS calibration, quantitative PV data, comparable to those obtained with a flow cell, can be provided by the 3M IR card. With the analytical protocol preprogrammed, the disposable 3M card provides a simple, rapid and convenient means of carrying out PV analyses, suitable for quality control laboratories, taking about 2–3 min per analysis.     

A rapid attenuated total reflectance infrared method for tolylene diisocyanate isomer ratio determination

An attenuated total reflectance (ATR) infrared method is described for the determination of the 2,4-/2,6-isomer ratio in tolylene diisocyanate. The absorption band intensity ratio at 1076 cm^?1 (2,4-isomer) and 780 cm^?1 (2,6-isomer) is measured.     

A rapid attenuated total reflectance infrared method for tolylene diisocyanate isomer ratio determination

An attenuated total reflectance (ATR) infrared method is described for the determination of the 2,4-/2,6-isomer ratio in tolylene diisocyanate. The absorption band intensity ratio at 1076 cm^?1 (2,4-isomer) and 780 cm^?1 (2,6-isomer) is measured.