ABSTRACT
We report a comprehensive kinetic and product study of the oxidation of mandelic acid (MA) by permanganate in the pH range of 1-13, including a full account of total oxidizing equivalents (five and three-electron change in acidic and basic media, respectively). In the entire pH range, the reaction shows a primary kinetic deuterium isotope effect (kH/kD ≥8-9), indicating rate-limiting hydride transfer. The deuterium label in α-deutero-mandelic acid is retained in benzaldehyde. Benzaldehyde (BZ) is formed in post-rate limiting steps due to reactions involving manganese intermediates. In alkaline pH (≥13), in the presence of barium acetate, Mn(VI) is removed as insoluble blue barium manganate; the stoichiometry of the first step of reduction was found to be: MA + 2Mn(VII) â PGA + 2Mn(VI). Manganate, MnO42-, is directly reduced to MnO2 giving an additional mole of phenylglyoxylic acid (PGA). The experimentally observed ratio of benzaldehyde to phenylglyoxylic (BZ/PGA) provides a basis for discrimination between mechanistic choices that include direct reduction of Mn(V) to Mn(III) (in an acidic medium), disproportionation to Mn(IV) and Mn(VI) or oxidation to Mn(VI) by a second mole of permanganate. Interestingly, at pH 4, a stoichiometric, soluble Mn(IV) is observed for the first time for hydroxy-acid oxidation, reminiscent of the Guyard reaction. Because of the widespread use of permanganate as an environmentally green oxidant, results from mandelic acid oxidation have implications for the remediation of dissolved organic matter (DOM) including hydrocarbons and nitroaromatics in waste and groundwater.
ABSTRACT
Identifying and implementing techniques for carbon management has become an important endeavor in the mitigation of global climate change. Two important techniques being pursued are geologic and terrestrial carbon sequestration. With regard to terrestrial sequestration, in order to accurately monitor changes in soil carbon potentially induced by sequestration practices, rapid, cost-effective, and accurate measurements must be developed. Spark-induced breakdown spectroscopy (SIBS) has the potential to be used as a field-deployable method to monitor changes in the concentration of carbon in soil. SIBS spectra in the 248 nm region of eight soils were collected, and the neutral carbon line at 247.85 nm was compared to total carbon concentration determined by standard dry combustion techniques. Additionally, Fe and Si emission lines were evaluated in a multivariate statistical model to evaluate their impacts on the model's predictive power for total carbon concentrations. The preliminary results indicate that SIBS is a viable method to quantify total carbon levels in soils, obtaining a correlation of (R(2)=0.972) between measured and predicated carbon in soils. These results show that multivariate analysis can be used to construct a calibration model for SIBS soil spectra.
