A flow-based procedure exploiting the lab-in-syringe approach for the determination of ester content in biodiesel and...

The ester content is an important parameter to be monitored in biodiesel for evaluation of the transesterification reaction yield and for assessing the purity of the final product. This is also a relevant quality parameter in diesel/biodiesel blends to avoid frauds, because legislation establishes a minimum amount of biodiesel to be added to diesel. The official method EN14103 requires the addition of an alternative internal standard (methyl nonadecanoate) for analysis of biodiesel from bovine tallow because the methyl heptadecanoate is found in high amounts in this product. In this work, it is proposed a fast, simple, practical, and environmental friendly flow-based spectrophotometric procedure, which exploits the formation of the violet complex between Fe(III) and the hydroxamate generated by the reactions of the alkyl esters with hydroxylamine. All involved steps are carried out inside the syringe pump of a sequential injection analyzer (lab-in-syringe approach). A single phase is attained by using ethanol as mediator solvent between the organic sample and aqueous soluble reagents. Linear responses for biodiesel samples and diesel/biodiesel blends were obtained from 4-99%(v/v) to 2.0-40%(v/v) methyl esters, described by the equations: A = 0.342 + 0.00305C (r = 0.997) and A = 0.174 + 0.00503C (r = 0.999), respectively. The analytical curve can be obtained by in-line dilution of a methyl linoleate stock solution. For biodiesel samples, the coefficient of variation (n = 10), limit of detection (99.7% confidence level), and sampling rate were estimated at 0.8%, 0.36%(v/v), and 15h^-1, respectively, whereas the corresponding values for the blend samples were 0.20%, 0.03%(v/v), and 12h^-1, respectively. The procedure consumes only 860μg of hydroxylamine, 366μg of Fe₂(SO₄)₃·H₂O, and 2.0mL ethanol and generates ca. 3.0mL of residue per determination. The results agreed with those obtained by official methods EN14103/2011 e EN14078, at the 95% confidence level.