Rapid quantitative determination of free fatty acids in fats and oils by fourier transform infrared spectroscopy

Rapid direct and indirect Fourier transform infrared (FTIR) spectroscopic methods were developed for the determination of free fatty acids (FFA) in fats and oils based on both transmission and attenuated total reflectance approaches, covering an analytical range of 0.2–8% FFA. Calibration curves were prepared by adding oleic acid to the oil chosen for analysis and measuring the C=O band @ 1711 cm^–1 after ratioing the sample spectrum against that of the same oil free of fatty acids. For fats and oils that may have undergone significant thermal stress or extensive oxidation, an indirect method was developed in which 1% KOH/methanol is used to extract the FFAs and convert them to their potassium salts. The carboxylate anion absorbs @ 1570 cm^–1, well away from interfering absorptions of carbonyl-containing oxidation end products that are commonly present in oxidized oils. Both approaches gave results comparable in precision and accuracy to that of the American Oil Chemists’ Society reference titration method. Through macroprogramming, the FFA analysis procedure was completely automated, making it suitable for routine quality control applications. As such, the method requires no knowledge of FTIR spectroscopy on the part of the operator, and an analysis takes less than 2 min.     

Rice bran FFA determination by diffuse reflectance IR spectroscopy

Rice bran with FFA levels above 0.1% cannot be used as a food ingredient due to oxidative off-flavor formation. However, extracting high FFA oil from bran by in situ methanolic esterification of rice bran oil to produce methyl ester biodiesel produces greater yields relative to low-FFA rice bran oil. Therefore, high-FFA bran could be exploited for biodiesel production. This study describes an FTIR spectroscopic method to measure rice bran FFA rapidly. Commercial rice bran was incubated at 37°C and 70% humidity for a 13-d incubation period. Diffuse reflectance IR Fourier transform spectra of the bran were obtained and the percentage of FFA was determined by extraction and acid/base titration throughout this period. Partial least squares (PLS) regression and a calibration/validation analysis were done using the IR spectral regions 4000-400 cm⁻¹ and 1731-1631 cm⁻¹. The diffuse reflectance IR Fourier transform spectra indicated an increasing FFA carbonyl response at the expense of the ester peak during incubation, and the regression coefficients obtained by PLS analysis also demonstrated that these functional groups and the carboxyl ion were important in predicting FFA levels. FFA rice bran changes also could be observed qualitatively by visual examination of the spectra. Calibration models obtained using the spectral regions 4000-400 cm⁻¹ and 1731-1631 cm⁻¹ produced correlation coefficients R and root mean square error (RMSE) of cross-validation of R=0.99, RMSE=1.78, and R=0.92, RMSE=4.67, respectively. Validation model statistics using the 4000-400 cm⁻¹ and 1731-1631 cm⁻¹ ranges were R=0.96, RMSE=3.64, and R=0.88, RMSE=5.80, respectively.     

Differentiation of Lard From Other Edible Fats and Oils by Means of Fourier Transform Infrared Spectroscopy and Chemometrics

Fourier transform infrared (FTIR) spectra at mid infrared regions (4,000–650 cm⁻¹) of lard and 16 edible fats and oils were compared and differentiated. The chemometrics of principal component analysis and cluster analysis (CA) was used for such differentiation using FTIR spectra intensities of evaluated fats and oils. With PCA, an “eigenvalue” of about 90% was achieved using four principal components (PCs) of variables (FTIR spectra absorbances at the selected frequency regions). PC1 accounted for 44.1% of the variation, while PC2 described 30.2% of the variation. The main frequency regions that influence the separation of lard from other evaluated fats and oils based on PC1 are 2,852.8 followed by 2,922 and 1,464.7 cm⁻¹. Furthermore, CA can classify lard into its group based on Euclidean distance.     

New FTIR method for the determination of FFA in oils

A rapid, practical, and accurate FTIR method for the determination of FFA in edible oils was developed. Analogous to the AOCS titration procedure, the FTIR FFA determination is effected by an acid/base reaction but directly measures the product formed rather than utilizing an end point based on an electrode potential or color change. A suspension of a weak base, potassium phthalimide (K-phthal) in 1-propanol (1-PrOH), is used to convert the FFA present in oils to their carboxylate salt without causing oil saponification, and differential spectroscopy is used to circumvent matrix effects. Samples are first diluted with 1-PrOH, then split, with one-half treated with the K-phthal reagent and the other half with 1-PrOH (blank reagent), their spectra collected, and differential spectra obtained to ratio out the invariant spectral contributions from the oil sample. Quantification of the percentage of FFA in the oil, expressed as %oleic acid, based on measurement of the peak height of the ν (COO⁻) absorption of the FFA salt formed, yielded a calibration with an SE of <0.020% FFA over the range of 0–4%. The method was validated by standard addition and the analysis of Smalley check samples, the results indicating that the analytical performance of the FTIR procedure is as good as or better than that of the standard titrimetric procedure. As structured, the FTIR procedure is a primary method, as calibration is not dependent on reference values provided by another method, and has performance criteria that could lead to its consideration as an instrumental AOCS procedure for FFA determination. The FTIR portion of the analysis is automatable, and a system capable of analyzing ∼60 samples/h was developed that could be of benefit to laboratories that carry out a large number of FFA analyses per day.     

Application of a Handheld Portable Mid-Infrared Sensor for Monitoring Oil Oxidative Stability

This study evaluated the capabilities of a handheld mid-infrared (MIR) spectrometer combined with multivariate analysis to characterize oils, monitor chemical processes occurring during oxidation, and to determine fatty acid composition. Vegetable oils (corn, peanut, sunflower, safflower, cottonseed, and canola) were stored at 65 °C for 30 days to accelerate oxidation reactions. Aliquots were drawn at 5 day intervals and analyzed by benchtop and portable handheld mid-infrared devices (4,000–700 cm⁻¹) and reference methods (IUPAC 2301 [1], 2302 [1]; AOCS Cd 8-58 [2]; and Shipe 1979 [3]). PLSR and soft independent modeling of class analogy (SIMCA) models were developed for oil classification and estimation of oil stability parameters. Models developed from MIR spectra obtained with a benchtop spectrometer equipped with a 3-bounce ATR device resulted in superior discriminative performances for classifying oils as compared to those obtained from handheld spectra (single-bounce ATR). Models developed from reference tests and handheld spectra showed prediction errors (SECV) of 1 meq/kg for peroxide value, 0.09% for acid value and 2% for determination of unsaturated fatty acids in different oils. Spectral regions ~3,012–2,850 cm⁻¹ (C–H stretching bands/shoulders of fatty acids), ~1,740 cm⁻¹ (C=O stretching of esters), and ~1,114 cm⁻¹ (–C–O stretching) were found to be important for prediction. Handheld-FTIR instruments combined with multivariate-analysis showed promise for determination of oil quality parameters. Portability and ease-of-use makes the handheld device a great alternative to traditional methods.     

Stoichiometric determination of hydroperoxides in fats and oils by fourier transform infrared spectroscopy

A primary Fourier transform infrared (FTIR) spectroscopic method for the determination of peroxide value (PV) in edible oils was developed based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Accurate quantitation of the TPPO formed in this reaction by measurement of its intense absorption band at 542 cm⁻¹ provides a simple means of determining PV. A calibration was developed with TPPO as the standard; its concentration, expressed in terms of PV, covered a range of 0–15 PV. The resulting calibration was linear over the analytical range and had a standard deviation of ±0.05 PV. A standardized analytical protocol was developed, consisting of adding ∼0.2 g of a 33% (w/w) stock solution of TPP in hexanol to ∼30 g of melted fat or oil, shaking the sample, and scanning it in a 100-μm KCI IR transmission cell maintained at 80°C. The FTIR spectrometer was programmed in Visual Basic to automate scanning and quantitation, with the reaction/FTIR analysis taking about 2 min per sample. The method was validated by comparing the analytical results of the AOCS PV method to those of the automated FTIR procedure by using both oxidized oils and oils spiked with tert-butyl hydroperoxide. The two methods correlated well. The reproducibility of the FTIR method was superior (±0.18) to that of the standard chemical method (±0.89 PV). The FTIR method is a significant improvement over the standard AOCS method in terms of analytical time and effort and avoids solvent and reagent disposal problems. Based on its simple stoichiometry, rapid and complete reaction, and the singular band that characterizes the end product, the TPP/TPPO reaction coupled with a programmable FTIR spectrometer provides a rapid and efficient means of determining PV that is especially suited for routine quality control applications in the fats and oils industry.     

Influence of triacylglycerol characterics on the determination of free fatty acids in vegetable oils by fourier transform infrared spectroscopy

A rapid and direct Fourier transform infrared (FTIR) spectroscopic method using a 25-μm NaCl transmission cell was developed for the determination of free fatty acids (FFA) in six important vegetable oils (corn, soybean, sunflower, palm, palm kernel, and coconut oils) that differ in fatty acid profile. The calibrations were established by adding either standard FFA (oleic, lauric acids) or a representative mixture of FFA obtained after saponification of the refined oils. For all oils, up to a FFA level of 6.5% for coconut oil, the best correlation coefficient was obtained by linear regression of the free carboxyl absorption at 1711 cm⁻¹. All correlation coefficients were greater than 0.993, and no significant difference between the calibration methods could be detected. Upon validation of the calibration, no significant difference (α=0.05) between the “actual” and the “FTIR predicted” FFA values could be observed. The calibration models developed for the six oils differed significantly and indicate the need to develop a calibration that is specific for each oil. In terms of repeatability and accuracy, the FTIR method developed was excellent. Because of its simplicity, quick analysis time of less than 2 min, and minimal use of solvents and labor, the introduction of FTIR spectroscopy into laboratory routine for FFA determination should be considered.     

Novel method for rapid monitoring of lipid oxidation by FTIR spectroscopy using disposable IR cards

A new FTIR approach was investigated for assessing edible oil oxidative stability with the use of polymer IR (PIR) cards as sample holders. This approach allows oil oxidation to be monitored at moderate temperatures owing to the fairly rapid rate at which unsaturated oils oxidize on the PIR cards. To assess the FTIR/PIR card method, pure TAG—triolein, trilinolein, and trilinolenin—were loaded onto cards and placed in a chamber where warm air (55°C) flowed over them continuously to facilitate oxidation. At periodic intervals, individual cards were removed and their FTIR spectra scanned, after which they were replaced in the aeration chamber. All spectra were normalized to compensate for variations in PIR card path lengths or oil loadings, and for each card the initial spectrum recorded (t=0) was subtracted from all subsequent spectra taken over time to produce differential spectra. With the use of a peak-find algorithm, the absorbance minimum in the cis region (3017–3000 cm⁻¹) and the absorbance maxima in the hydroperoxide (3550–3200 cm⁻¹), isolated trans (977–957 cm⁻¹), and conjugated trans regions (995–983 cm⁻¹) were measured in the differential spectra and plotted as a function of time. For all three TAG, the loss of cis double bonds was linearly related to the development of hydroperoxides and isolated trans bonds for much of the oxidation process, whereas for the polyunsaturated TAG a similar relationship also existed for conjugated trans species. Based on experimentally determined hydroperoxide (ROOH) absorbance slope factor (0.06 mAbs/PV), ROOH absorbance changes were converted to PV, allowing direct PV monitoring as a function of time using the PIR cards. Trilinolenin, trilinolein, and triolein attained a PV of 100 mequiv/kg oil after, 43,98, and 2889 min, respectively, their relative reaction rates being similar to ratios published in the literature. The assessment of the FTIR/PIR card method using TAG indicates that it may be a practical and rapid means of oxidizing lipids and tracking their oxidative state in terms of PV so as to provide a measure of their oxidative stability.     

In situ IR,Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation

The application of in situ Raman, IR, and UV-Vis DRS spectroscopies during steady-state methanol oxidation has demonstrated that the molecular structures of surface vanadium oxide species supported on metal oxides are very sensitive to the coordination and H-bonding effects of adsorbed methoxy surface species. Specifically, a decrease in the intensity of spectral bands associated with the fully oxidized surface (V⁵⁺) vanadia active phase occurred in all three studied spectroscopies during methanol oxidation. The terminal V = O (∼1030 cm⁻¹) and bridging V–O–V (∼900–940 cm⁻¹) vibrational bands also shifted toward lower frequency, while the in situ UV-Vis DRS spectra exhibited shifts in the surface V⁵⁺ LMCT band (>25,000 cm⁻¹) to higher edge energies. The magnitude of these distortions correlates with the concentration of adsorbed methoxy intermediates and is most severe at lower temperatures and higher methanol partial pressures, where the surface methoxy concentrations are greatest. Conversely, spectral changes caused by actual reductions in surface vanadia (V⁵⁺) species to reduced phases (V³⁺/V⁴⁺) would have been more severe at higher temperatures. Moreover, the catalyst (vanadia/silica) exhibiting the greatest shift in UV-Vis DRS edge energy did not exhibit any bands from reduced V³⁺/V⁴⁺ phases in the d–d transition region (10,000–30,000 cm⁻¹), even though d–d transitions were detected in vanadia/alumina and vanadia/zirconia catalysts. Therefore, V⁵⁺ spectral signals are generally not representative of the percent vanadia reduction during the methanol oxidation redox cycle, although estimates made from the high temperature, low methoxy surface coverage IR spectra suggest that the catalyst surfaces remain mostly oxidized during steady-state methanol oxidation (15–25% vanadia reduction). Finally, adsorbed surface methoxy intermediate species were easily detected with in situ IR spectroscopy during methanol oxidation in the C–H stretching region (2800–3000 cm⁻¹) for all studied catalysts, the vibrations occurring at different frequencies depending on the specific metal oxide upon which they chemisorb. However, methoxy bands were only found in a few cases using in situ Raman spectroscopy due to the sensitivity of the Raman scattering cross-sections to the specific substrate onto which the surface methoxy species are adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

The determination of peroxide value by fourier transform infrared spectroscopy

A rapid method for the quantitative determination of peroxide value (PV) of vegetable oils by Fourier transform infrared (FTIR) transmission spectroscopy is described. Calibration standards were prepared by the addition oft-butyl hydroperoxide to a series of vegetable oils, along with random amounts of oleic acid and water. Additional standards were derived through the addition of mono- and diglyceride spectral contributions, as well as zero PV spectra obtained from deuterated oils. A partial least squares (PLS) calibration model for the prediction of PV was developed based on the spectral range 3750–3150 cm⁻¹. Validation of the method was carried out by comparing the PV of a series of vegetable oils predicted by the PLS model to the values obtained by the American Oil Chemists Society iodometric method. The reproducibility of the FTIR method [coefficient of variation (CV)=5%)] was found to be better than that of the chemical method (CV =9%), although its accuracy was limited by the reproducibility of the chemical method. The method, as structured, makes use of a 1-mm CaF₂ flow cell to allow rapid sample handling by aspiration. The spectrometer was preprogrammed in Visual Basic to guide the operator in performing the analysis so that no knowledge of FTIR spectroscopy is required to implement the method. The method would be suitable for PV determinations in the edible oil industry and takes an average of three minutes per sample.     

Rapid Method for the Determination of Moisture Content in Biodiesel Using FTIR Spectroscopy

A new, rapid, and direct method was developed for the determination of moisture content in biodiesel produced from various types of oils using Fourier transform infrared (FTIR) spectroscopy with an attenuated total reflectance (ATR) element. Samples of biodiesels used in this study were produced using sludge palm oil (SPO). The calibration set was prepared by spiking double-distilled water into dried biodiesel samples in ratios (w/w) between 0 and 10% moisture. Absorbance values from the wavelength regions 3,700–3,075 and 1,700–1,500 cm⁻¹, and the partial least square (PLS) regression method were used to derive a FTIR spectroscopic calibration model for moisture content in biodiesel samples. The coefficient of determinations (R ²) for the models was computed by comparing the results obtained from FTIR spectroscopy against the values of the moisture concentrations (%) determined using the American Oil Chemists’ Society (AOCS) oven method Ca 2d-25. Same comparison was done using International Union of Pure and Applied Chemistry (IUPAC) distillation method 2.602. R ² was 0.9793 and 0.9700 using AOCS and IUPAC methods, respectively. The standard error (SE) of calibration was 1.84. The calibration model was cross validated within the same set of samples, and the standard deviation (SD) of the difference for repeatability (SDDr) and accuracy (SDDa) of the FTIR method was determined. With its speed and ease of data manipulation, FTIR spectroscopy is a useful alternative method to other methods for rapid and routine determination of moisture content in biodiesel for quality control.     

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).     

Evaluation of Biodiesel Derived from <Emphasis Type="Italic">Camelina sativa</Emphasis> Oil

Biodiesel derived from camelina as well as other feedstocks including palm, mustard, coconut, sunflower, soybean and canola were prepared via the conventional base-catalyzed transesterification with methanol. Fatty acid profiles and the fuel properties of biodiesel from different vegetable oils were analyzed and tested in accordance with ASTM D6751. Camelina biodiesel contains 10–12%, 37–40%, and 48–50% saturated, monounsaturated and polyunsaturated components, respectively. Some fuel properties of camelina biodiesel are comparable to that of sunflower biodiesel including kinematic viscosity (40 °C), flash point, cloud point, cold filter plugging point, and oil stability index. However, camelina biodiesel exhibited the poorest oxidative stability, highest distillation temperature and has the highest potential to form coke during combustion, all of which are attributed to the high amounts of n-3-fatty acids in camelina oil. While neat camelina biodiesel may exhibit undesirable fuel properties, it is very comparable with soybean biodiesel at the B20 level.     

Free fatty acid formation and lipid oxidation on milled rice

Milled rice was stored at 37°C and 70% humidity and sampled regularly for 50 d. Rice surface lipid was extracted with isopropanol and analyzed for free fatty acids (FFA) and conjugated diene (CD) contents. Diffuse reflectance Fourier transform infrared (DRIFTS) spectra of the rice samples were also obtained. FFA and CD levels increased together during rice storage and exhibited three distinct phases. DRIFTS identified a decrease in intensity at 1746 cm⁻¹ (ester, −C=O) and increases in intensity at 1731 cm⁻¹ (aldehyde, −CO) and 1714 cm⁻¹ (fatty acid, −C=O) during storage, which correlated well with the chemical analysis data. DRIFTS spectral data were analyzed by a partial least squares regression method to identify spectral regions that correlate strongly with measured FFA and construct prediction models. Overall, the mid-infrared region (4000–400 cm¹) gave the best model (R=0.98, root mean square error of cross-validation=0.05) and also predcted the FFA content of milled rice well. The DRIFTS technique has potential for use in studying qualitative chemical changes on the milled rice surface lipids and for predicting FFA on milled rice.     

Determining the blend level of mixtures of biodiesel with conventional diesel fuel by fiber-optic near-infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy

Biodiesel, defined as the alkyl esters (usually methyl esters) of vegetable oils, is miscible with conventional diesel fuel at all blend levels. Until the present time, no rapid and reliable analytical method has existed for determining the blend level of biodiesel in conventional diesel fuel. In the present work, near-infrared (NIR) and nuclear magnetic resonance (NMR) spectroscopies were used to determine the blend level of biodiesel in conventional diesel fuel. Several regions in the NIR region (around 6005 cm⁻¹ and 4800–4600 cm⁻¹) are suitable for this purpose. The method is rapid and easy to use, and does not require any hardware changes when using the same instrument for monitoring the biodiesel-producing transesterification reaction and determining biodiesel fuel quality. In ¹H NMR spectroscopy, the integration values of the peaks of the methyl ester moiety and the aliphatic hydrocarbon protons in biodiesel and conventional diesel fuel were used for determining blend levels. The results of NIR and NMR blend level determinations are in good agreement.     

Determination of the length of polymethylene chains in salts of saturated and unsaturated fatty acids by infrared spectroscopy

The length of polymethylene chains is determined by counting the number of, or measuring the position of, methylene vibration peaks in the 1070–710 cm⁻¹ and/or the 1380–1170cm⁻¹ regions of the IR spectrum of salts of fatty acids. Plotting this peak position against the phase relationship of the vibration in adjacent methylenes gives a curve which is independent of the chain length. (Thephase relationship, Φ/π=k/(m+1); where φ is the phase difference in radians between adjacent methylenes in a chain;m is the number of methylenes in the chain;k=1,2,3,…m, withk=1 generally assigned to the in-phase vibration.) Separate curves are obtained for methylene wagging and for two arrays of coupled twisting-rocking vibrations. Coupled twisting-rocking vibrations give as many as one peak per methylene group in the 1070–710 cm⁻¹ region with silver, sodium, potassium and barium salts of saturated acids. Lead salt peaks split. These peaks show the total length of salts of both saturated andtrans-unsaturated acids, but only the length of the carboxylate segment in salts ofcis-unsaturated acids. (The carboxylate segment comprises the carbons from the carboxylate carbon to the first unsaturated carbon, inclusive.) Wagging vibrations in the 1380–1170 cm⁻¹ region show the total chain length of saturated salts and the length of the carboxylate segment in unsaturated salts, bothcis andtrans. This region also has peaks for twisting-rocking vibrations, and they are most conspicuous in the spectra of silver and barium salts. Presented in part at the AOCS meeting in Toronto, Canada, 1962.     

Reduction of Free Fatty Acids in Acidic Nonedible Oils by Modified K10 Clay

Biodiesel is a biofuel obtained from vegetable oils. The oils used as raw materials are usually refined edible vegetable oils. Nonedible acidic oils are unsuitable for biodiesel production unless reduction of the high content in free fatty acids (FFA) of these materials had been achieved. Obtaining a good raw material from unprofitable oils becomes an important research field. Additionally clays have a long history in industrial sorption and catalysis, some being commercially available and with properties that can be modified. In this work we present the results of the use of the montmorillonite clay K10 and two acid modified clays K10(I) and K10(II), in the esterification of stearic acid with methanol and 95 % of methyl stearate was obtained with K10(II). These clays were then used for the first time to reduce the acidity of enhanced FFA sunflower oil and they show to be very effective. Reduction of FFA from 11 to 4 % was obtained with K10(II) mainly due to 94 % conversion of FFA into fatty acid methyl esters (FAME). These clays were also tested with two waste oils, one from domestic use and the other gathered from different restaurants, and showed their ability to lower the acidity of these oils. Reactions were followed by ¹H NMR as well as quantitative determination of FFA and FAME. Clays were characterized by FTIR and XRD.     

Application of a Portable Handheld Infrared Spectrometer for Quantitation of <Emphasis Type="Italic">trans</Emphasis> Fat in Edible Oils

Trans fat poses serious health risks to consumers. In order to meet the FDA labeling requirements for trans fatty acids, development of fast, accurate, easy-to-use analytical methods for oils, fats and related products is desirable. Fourier transform infrared spectroscopy (FTIR) is a well-established analytical technique for quantifying trans fats, and the development of handheld FTIR units over the past decade presents new application opportunities. Our objective was to evaluate the performance of a handheld FTIR sensor for measuring trans fat content between 0.1 and 20% trans (w/w) in edible saturated and unsaturated oils. Calibration models were built by measuring height of the band at 966 cm⁻¹ and by partial least squares regression (PLSR) using benchtop FTIR as a reference method. Predictive accuracy of the models was validated with an independent test set of commercial edible oils. Calibration models developed using PLSR and linear regression of band heights gave correlation coefficients R ² > 0.98. Multivariate analysis for the handheld unit gave standard error of prediction (SEP) of approximately 1%, comparable to values obtained with benchtop systems. This study demonstrates that handheld FTIR spectroscopy coupled with chemometrics is a suitable method for quantitation of trans fat content.     

Analysis of oxidation states of vanadium in vanadia–titania catalysts by the IR spectra of adsorbed NO

Adsorption of NO on vanadia–titania samples pre-subjected to different reduction treatments has been studied by FTIR spectroscopy. When the NO adsorption is performed at 85 K on oxidized samples, antisymmetric NONO species, typical for V⁵⁺ sites, are detected and characterized by bands at 1779 and 1686 cm⁻¹. At ambient temperature, however, adsorption is negligible and only with time reactive adsorption occurs producing NO⁺ (2120 cm⁻¹), nitro/nitrato species (bands in the 1650–1100 cm⁻¹ region) and weakly adsorbed NO (broad band at 1915 cm⁻¹). Adsorption of NO at ambient temperature on reduced samples results in the formation of two types of species: (i) V⁴⁺(NO)₂ dinitrosyls characterized by ν_s(NO) and ν_as(NO) at 1903–1880 and 1769–1753 cm⁻¹, respectively, and (ii) V³⁺(NO)₂ complexes, which give rise to ν_s(NO) at 1834–1822 cm⁻¹ and ν_as(NO) at 1697–1685 cm⁻¹. At low temperature the dinitrosyls are transformed into species in which more than one (NO)₂ dimer is attached to one cationic site. Addition of O₂ to NO, preadsorbed on reduced vanadia–titania samples, results in a fast oxidation of the V³⁺(NO)₂ species, whereas the V⁴⁺(NO)₂ complexes are more stable and do not disappear completely in the presence of oxygen. The results obtained suggest that NO is a convenient probe molecule for the analysis of the oxidation state of vanadium in vanadia–titania catalysts. To prevent oxidation of reduced vanadium sites, low equilibrium pressures of NO and registration of the IR spectrum soon after the NO admission are recommended. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electro-Catalytic Oxidation of Methanol on a Ni–Cu Alloy in Alkaline Medium

The electro-catalytic oxidation of methanol on a Ni–Cu alloy (NCA) with atomic ratio of 60/40 having previously undergone 50 potential sweep cycles in the range 0–600 mV vs. (Ag/AgCl) in 1 m NaOH was studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS). The electro-oxidation was observed as large anodic peaks both in the anodic and early stages of the cathodic direction of potential sweep around 420 mV vs. (Ag/AgCl). The electro-catalytic surface was at least an order of magnitude superior to a pure nickel electrode for methanol oxidation. The diffusion coefficient and apparent rate constant of methanol oxidation were found to be 2.16 × 10⁻⁴ cm² s⁻¹ and 1979.01 cm³ mol⁻¹ s⁻¹, respectively. EIS studies were employed to unveil the charge transfer rate as well as the electrical characteristics of the catalytic surface. For the electrochemical oxidation of methanol at 5.0 m concentration, charge transfer resistance of nearly 111 Ω was obtained while the resistance of the electro-catalyst layer was ca. 329 Ω.