Insights on thermodynamic thermal properties and infrared spectroscopic band assignments of gallic acid.

Gallic acid (3,4,5-trihydroxybenzoic acid) is a popular nutraceutical found in various natural sources. A confusion regarding its thermodynamic properties, e.g., melting point, can be detected in the reported literature values. Similar issues exist for the assignment of its spectroscopic bands in the region of hydroxyl stretching vibrations. In this study, thermal analysis techniques, infrared spectroscopy and X-ray diffraction were used to study the thermal behavior of gallic acid. It is shown that gallic acid exhibits various thermochemical transitions (solid-solid and solid-liquid transitions). The value of the specific heat of the thermal transition around 90 °C indicates that this effect is not only related to water removal, but to decomposition. The absence of significant/exclusive water removal at 90 °C suggests that water being present in the structure of gallic acid is strongly bounded, while the main pathway for the decomposition around 90 °C seems to be the dehydration through esterification reaction between -COOH and -OH groups of gallic acid. Recrystallization of gallic acid from methanol-heavy water solvent mixture, leads to the incorporation of heavy water in its structure. The comparative evaluation of the recrystallized and raw gallic acid allows for a proper spectroscopic band assignment of various vibrations. The thermal effect around 260 °C is a typical thermochemical transition and not a melting point. The extensive polymorphism of gallic acid and the respective solid-solid transformations are also related to partial decomposition.

Post-treatment of molasses wastewater by electrocoagulation and process optimization through response surface analysis.

Molasses wastewater is a high strength effluent of food industry such as distilleries, sugar and yeast production plants etc. It is characterized by a dark brown color and exhibits a high content in substances of recalcitrant nature such as melanoidins. In this study, electrocoagulation (EC) was studied as a post treatment step for biologically treated molasses wastewater with high nitrogen content obtained from a baker's yeast industry. Iron and copper electrodes were used in various forms; the influence and interaction of current density, molasses wastewater dilution, and reaction time, on COD, color, ammonium and nitrate removal rates and operating cost were studied and optimized through Box Behnken's response surface analysis. Reaction time varied from 0.5 to 4 h, current density varied from 5 to 40 mA/cm(2) and dilution from 0 to 90% (v/v expressed as water concentration). pH, conductivity and temperature measurements were also carried out during each experiment. From preliminary experiments, it was concluded that the application of aeration and sample dilution, considerably influenced the kinetics of the process. The obtained results showed that COD removal varied between 10 and 54%, corresponding to an operation cost ranging from 0.2 to 33 euro/kg COD removed. Significant removal rates were obtained for nitrogen as nitrate and ammonium (i.e. 70% ammonium removal). A linear relation of COD and ammonium to the design parameters was observed, while operation cost and nitrate removal responded in a curvilinear function. A low ratio of electrode surface to treated volume was used, associated to a low investment cost; in addition, iron wastes could be utilized as low cost electrodes i.e. iron fillings from lathes, aiming to a low operation cost due to electrodes replacement. In general, electrocoagulation proved to be an effective and low cost process for biologically treated molasses-wastewater treatment for additional removal of COD and nitrogen content and color reduction. Treated effluent samples with good quality were produced by EC, with COD, NH4-N and NO3-N concentrations of 180, 52 and 2 mg/l respectively. Response surface analysis revealed that optimized conditions could be established under moderate molasses wastewater dilution, (e.g. 45%), at 3.5 h treatment time and 33 mA/cm(2) current density.