Monitoring tert-Butylhydroquinone Content and Its Effect on a Biolubricant during Oxidation.

The use of biolubricants as a replacement for petroleum-based products is becoming more and more important, due to the current global energy and crude oil scenario. Thus, the production of biolubricants (which could take place in biorefineries) should be as efficient as possible, obtaining high-quality products with suitable viscosity or oxidation stability values to compete with oil refineries. One of the ways to produce biolubricants is through double transesterification from vegetable oils, where the role of catalysts (usually homogeneous) is vital, as they can improve the yield of the process. However, they should be removed after the chemical reaction, which is difficult once the biolubricant is obtained. Otherwise, they could act as catalysts during oxidation, contributing to a further decrease in oxidation stability and provoking significant changes. To avoid this, antioxidant addition could be an interesting choice. The aim of this work was to assess TBHQ addition in frying oil biolubricants, monitoring properties such as viscosity, acid number, absorbance or TBHQ content (through voltammetry) during oxidation. TBHQ addition (2114 mg·L-1) kept the main quality parameters during oxidation compared to control samples. In contrast, TBHQ content decreased during oxidation (to 160 mg·L-1), which proved its antioxidant effect.

Second-order advantage maintenance with voltammetric data modeling for quantitation of ethiofencarb in the presence of interferences.

This work presents the development of a method based on a voltammetric determination coupled to second-order data modeling with multivariate curve resolution-alternating least-square (MCR-ALS) and unfolded partial least squares regression followed by residual bilinearization (U-PLS/RBL) for the quantitation of the pesticide ethiofencarb in the presence of interferences in tap water. The determination of ethiofencarb by voltammetry is possible on the basis that this pesticide is hydrolysed in alkaline media giving rise to a compound which shows an oxidation peak at Ep=0.80 V. But some other pesticides belonging to the same family can be considered as interferences due to the high overlapping in their signals. The two such interferences are fenobucarb and bendiocarb, which have not been included in the calibration step. The possibility of second-order multivariate calibration was studied by using the hydrolysis time as the third variable, and MCR-ALS and U-PLS/RBL. Good results were obtained in this determination in spite of the high overlapping in voltammetric signals.