Room-temperature ultrasound-assisted digestion of biodiesel for stripping voltammetry of metals with adequate recovery values (94–108%) and low residual carbon content is demonstrated.

aIn this work, mid-infrared spectroscopy and multivariate control charts based on net analyte signal were applied for quality control of B5 blends of biodiesel/diesel (5% biodiesel/95% diesel). Control charts were constructed using instrumental signal decomposition, generating three charts: the net analyte signal chart for monitoring the analyte of interest (methyl soybean biodiesel); the interference chart, which corresponds to the contribution of all other compounds in the diesel sample (diesel); and the residual chart, which corresponds to non-systematic variations. Statistical limits were established for each developed chart, using samples inside quality specifications (normal operation conditions). To validate multivariate control charts, new samples were analyzed. The new samples represented samples in-control and samples out-of-control in relation to the content of biodiesel, adulterated biodiesel with severe vegetable oils and adulterated diesel with residual automotive lubricant oil, kerosene, and gasoline. The results obtained show an excellent distinction between the samples inside and out of the quality specifications, with 91% and 100% correctly classified, respectively, which demonstrates that the methodology developed is a viable alternative for quality monitoring of this type of fuel.

This thesis presents the use of ultrasonic radiation for the digestion of biodiesel samples (B100) for the determination of metal ions by electrochemical stripping techniques (potentiometric and voltammetric) using a glassy-carbon electrode modified with a mercury film. Biodiesel samples (50 mg) were subjected to digestion in glass tubes with a mixture of 3.0 mL of concentrated HCl and 4.4 ml H 2 O 2 (30%), placed in an ultrasonic bath (40 kHz and 120 W) exactly on the higher intensity region (piezoelectric) of the ultrasound and sonicated for 40 min at room temperature (~ 20°C). These parameters were optimized using the chemometric technique of factorial design for the analysis of biodiesel samples spiked with ethanolic standard solutions of zinc, cadmium, lead and copper. Recovery values between 97 and 107% were observed in the optimal conditions found to zinc, cadmium, lead and copper. Residual carbon content (RCC) values after digestions were in the range of 3.05 to 3.75%. The simultaneous determination of zinc, cadmium, lead and copper using anodic stripping voltammetry revealed limit of detection (LD) values of 44 ng kg-1 ; 30 ng kg-1 ; 145 ng kg-1 ; 96 ng kg-1 , respectively. Additionally, biodiesel samples (100 mg) were also treated in glass tubes with a mixture of 1.59 mL concentrated HCl and 3.0 ml H 2 O 2 (30%) under sonication of an ultrasonic probe (sonication time 12.5 min, 25% amplitude, pulse of 5.0 s and time interval of 2.0 s). The parameters were also optimized employing the chemometric technique of factorial design for the analysis of spiked samples. Recovery values between 95 and 104% were observed in the satisfactory condition for zinc, cadmium, lead and copper. RCC values after digestions comprised values between 0.43 to 0.54%. For the simultaneous determination of zinc, cadmium, lead and copper using anodic stripping voltammetry obtained in the digestates employing the ultrasonic probe, the LD values found respectively for zinc, cadmium and copper were 25 ng kg-1 and for lead 56 ng kg-1. All results obtained using assisted digestion by ultrasonic bath and / or ultrasonic probe indicate that the proposed methods for the biodiesel sample preparation presents a comparable performance to traditional methods of digestion using acid blends, or yet digestions assisted by microwave radiation.

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