A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to SN1 reactions.

The standard methods for analyzing solvent effects on chemical reactions largely include linear free energy relations that relate kinetic and spectroscopic terms to solvent interactive parameters. The number of these parameters has grown over the years in order to make linear free energy techniques more accurate and cover a wider range of reaction systems. However, even with the myriad of parameters, the details of specific reaction systems make the application of these techniques sometimes unreliable. On the other hand, a thermodynamic approach provides a more precise analysis, and has proven particularly useful for reactions in multi-component solvent systems. In this article we present the mathematical formalism for relating the activation free energy to the bulk thermodynamic properties for a binary (cosolvent) system. We then use this thermodynamic approach, coupled with selected solvent models, to analyze the hydrolysis rates of tert-butyl chloride in the acetonitrile/water solvent system under iso-mole fraction, isodielectric, and isothermal conditions. These analyses allow us to differentiate and quantify bulk electrostatic effects and the effects of close-range solute-solvent interactions.

Simple photoreduction of carbon dioxide to formic acid and true quantum yield.

There is a need to develop techniques for conversion of carbon dioxide to useful products such as formaldehyde, formic acid, methanol, and hydrocarbons. Carbon dioxide can be converted into these products using either photochemically, electrochemically, thermochemical or hydrogenation by bacteria. Formate is of interest due to the possibility of being used in liquid fuel cells, as an additive in pyrolysis vapors and as a precursor for biological fuels. In this work, conversion of carbon dioxide to formic acid under acidic conditions and formate under basic or neutral conditions was accomplished through photoreduction using an inexpensive setup consisting of titanium dioxide, metal phthalocyanines and inexpensive incandescent sources. The yield of formic acid based on anion chromatography was 1.54%. This work also discusses and presents a true quantum yield determined using chemical actinometry which was near 2.0%. Detailed studies of the photoreduction process showed that the amount of sensitizer, light intensity and pH affect the amount of formate generated.

Titania-hydroxypropyl cellulose thin films for the detection of peroxide vapors.

Titania nanoparticles in a hydroxypropyl cellulose matrix produced using a sol-gel method were utilized to prepare films on polycarbonate slides and coatings on cellulose papers. The exposure of these materials to hydrogen peroxide gas leads to the development of an intense yellow color. By using an inexpensive web camera and a tungsten lamp to measure the reflected light, first-order behavior in the color change was observed when exposed to peroxide vapor of less than 50 ppm. For 50 mass percent titania nanoparticles in hydroxypropyl cellulose films on polycarbonate, the detection limit was estimated to be 90 ppm after a 1 min measurement and 1.5 ppm after a 1 h integration. The coatings on the filter paper had a 3-fold higher sensitivity compared to the films, with a detection limit of 5.4 ppm peroxide for a 1 min measurement and 0.09 ppm peroxide for a 1 h integration. The high sensitivity and rapid response of these films make them a promising material for use as a sensitive peroxide detector.

Iron-rich Oklahoma clays as a natural source of chromium in monitoring wells.

Water samples, drawn from groundwater monitoring wells located southeast of Oklahoma City, OK, were found to contain elevated concentrations of total chromium with an apparent source localized to the area surrounding each well. Since these monitoring wells are located in areas with no historic chromium usage, industrial sources of chromium were ruled out. Water testing was performed on twelve monitoring wells in the area that historically had elevated total chromium concentrations ranging from 10-4900 micrograms per litre. Filtered water samples were found to be free of chromium contamination, indicating that the source of the chromium is the suspended solids. Analysis of these solids by acid digestion and a sequential extraction technique revealed that the chromium was primarily associated with iron-containing solids. X-ray diffraction identified goethite, an iron oxide hydroxide, as the dominant iron-containing phase in the suspended solids. The mineralogy in this region is dominated by interbedded red-bed sandstone and mudstone whose mineral content includes mixed-layer illite-smectite, hematite, goethite, gypsum and dolomite. Elemental analysis of soil samples collected as a function of depth in the locale of the monitoring wells indicated that the iron rich clays contain a natural source of chromium. The elevated levels of total chromium are most likely due to the dissolution of silica and alumina from the chromium containing iron clays in the basic well water, resulting in the release of fine suspended solids that naturally have high chromium concentrations. These results should be applicable to other areas containing iron-rich clays.

Follow-up study on the effects on well chemistry from biological and chemical remediation of chlorinated solvents.

The enduring effects of injected materials used for the remediation of chlorinated solvents were examined. Approximately two years previous to this study, four different remediation methods were tested in an area located southeast of Oklahoma City, OK. These methods included bioremediation under both anaerobic and aerobic conditions and chemical remediation using Fenton's reagent or KMnO(4). A series of water quality tests performed in this investigation revealed that the bioremediation processes did not introduce any unexpected chemistry. However, the wells that were treated anaerobically still had water with a negative oxidation-reduction potential and had no recontamination with migrating trichloroethylene as opposed to the aerobic wells that had both positive redox potentials and trichloroethylene present. Also, chemical treatment using Fenton's reagent did not result in any long-term changes in the well chemistry, with the exception of inducing a slight acidity. This is due to the facts that addition of iron into the aquifer that is already in contact with iron-rich clay soil had little long-term effects and the radical chemistry with hydrogen peroxide is short-lived due to its reactivity. KMnO(4)-based remediation results in deposition of new materials containing manganese in elevated oxidation states that may provide long-term protection against the build up of chlorinated organic compounds.