ABSTRACT
An application of the standard addition method to stripping voltammetry of solid materials immobilized in inert electrodes is described. The method allows the determination of the mass fraction of a depositable metal M in a material on addition of known amounts of a standard material containing M to a mixture of that material and a reference compound of a second depositable metal, R. After a reductive deposition step, voltammograms recorded for those modified electrodes immersed in a suitable electrolyte produce stripping peaks for the oxidation of the deposits of M and R. If no intermetallic effects appear the quotients between the peak areas and the peak currents for the stripping oxidation of M and R vary linearly with the mass ratio of the added standard and the reference compound, thus providing an electrochemical method for determining the amount of M in the sample. The method has been applied to the determination of Zr in minerals, ceramic frits, and pigments, using ZnO as reference material and ZrO(2) as the standard.
Subject(s)
Aluminum Oxide/chemistry , Electrochemistry/standards , Minerals/chemistry , Zirconium/analysis , Aluminum Oxide/standards , Calibration , Electrodes , Minerals/standards , Reference Standards , Sensitivity and Specificity , Zinc Oxide/chemistry , Zinc Oxide/standards , Zirconium/standardsABSTRACT
A methodology for quantifying calcium carbonate (875 and 712 cm(-1)) and silica (798 and 779 cm(-1)) by FTIR spectroscopy applying the constant ratio method is proposed. The studied method is applied for quantitative analysis of calcite and quartz in geological samples. The suggested method uses potassium ferricyanide (2115 cm(-1)) as standard and samples are prepared as potassium bromide pellets, with statistically satisfactory results (relative standard deviation less than 5%). The influence of particle size (pulverised samples) on the accuracy of the results found by FTIR spectroscopy applying the constant ratio method has been studied. The granulometric study suggests that the homogeneity of particle size is important. An absorbances correction method is proposed to correct spectral interferences. Due to the fact that most spectra are characterised by a high number of absorbance peaks, spectral interferences may occur so that some peaks cannot be used for quantitative analysis. These interferences can be evaluated and eliminated with the proposed method and the peaks can be used in the analysis.
ABSTRACT
The oxidative deterioration of polyunsaturated fatty acids (PUFAs) in culinary oils and fats during episodes of heating associated with normal usage (80-300 degrees C, 20-40 min) has been monitored by Fourier transform infrared spectroscopy (FTIR). The thermal oxidation of PUFAs is a free radical chain reaction, in which hydroperoxides are generally recognized as the primary major products. Hydroperoxides of PUFAs are easily decomposed into a very complex mixture of secondary products with the decrease in unsaturation. The oxidative advance of PUFAs during heating was studied by the determination of unsaturation percentage at different temperatures and heating times. Oils frequently used in food frying such as olive oil, sunflower oil, corn oil and seeds oil (sunflower, safflower and canola seed) were studied. The results show there is a decrease in unsaturation starting at 150 degrees C and becoming more pronounced at temperatures around 250 degrees C. The following variations were found in the unsaturation percentage, expressed as methyl linoleate, between the original sample and the sample heated at 300 degrees C for 40 min: olive oil (19-6%), sunflower oil (29-12%), corn oil (28-18%) and seeds oil (23-11%). This variation in unsaturation grade provides evidence of the transformation of essential PUFAs and subsequent decrease in the oils' nutritional value. The internal standard method is suitably precise when the n-valeronitrile is used as standard as shown by the 1-2% relative standard deviation (R.S.D.) found for seven replicates.
