Electrooxidation of the iodides [C(4)mim]I, LiI, NaI, KI, RbI, and CsI in the room temperature ionic liquid [C(4)mim][NTf2]

The electrochemical oxidation of 1-butyl-3-methylimidazolium iodide, [C(4)mim]I, has been investigated by cyclic voltammetry at a platinum microelectrode at varying concentrations in the RTIL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(4)mim][NTf2]. Two oxidation peaks were observed. The first peak is assigned to the oxidation of iodide to triiodide, in an overall two-electron process: 3I(-)- 2e(-) -> I-3(-). At higher potentials, the electrogenerated triiodide oxidizes to iodine, in an overall one-electron process: I-3(-) - e(-) -> 3/2I(2). An average diffusion coefficient, D, for I- of 1.55 x 10(-11) m(2) s(-1) was obtained. A digital simulation program was used to simulate the voltammetric response, and kinetic parameters were successfully extracted. The parameters deduced from the simulation include D for I-, I-3(-), and I-2 and K-eq,K-2, the equilibrium constant for the reaction of iodide and iodine to form triiodide. Values for these parameters are of the same order as those previously published for the oxidation of Br- in the same RTIL [Allen et al. J. Electroanal. Chem. 2005, 575, 311]. Next, the cyclic voltammetry of five different inorganic iodide salts was studied by dissolving small amounts of the solid in [C(4)mim][NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 0.55, 1.14, 1.23, 1.44, and 1.33 x 10(-11) m(2) s(-1) and solubilities of 714, 246, 54, 83, and 36 mM for LiI, NaI, KI, RbI, and CsI, respectively. The slightly smaller diffusion coefficients for the XI salts (compared to [C(4)mim]I) may indicate that I- is ion-paired with Li+, Na+, K+, Rb+, and Cs+ in the RTIL medium.

Electrochemical reduction of nitrobenzene and 4-nitrophenol in the room temperature ionic liquid [C(4)dmim][N(Tf)(2)]

The reductions of nitrobenzene and 4-nitrophenol were studied by cyclic voltammetry in the room temperature ionic liquid 1-butyl2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)dmim][N(Tf)(2)] on a gold microelectrode. Nitrobenzene was reduced reversibly by one electron and further by two electrons in a chemically irreversible step. The more complicated reduction of 4-nitrophenol revealed three reductive peaks (two irreversible and one reversible) which were successfully simulated using the digital simulation program DigiSim((R)) using a mechanism of rapid self-protonation, given below.

The Application of Digital Photogrammetric Techniques and Aerial Photography to the Preservation of Archaeological Detail. Case Study: The Copney Stone Circle Complex, Co. Tyrone, N. Ireland

The Copney Stone Circle Complex, Co. Tyrone, N. Ireland, is an important Bronze Age site forming part of the Mid-Ulster Stone Circle Complex. The Environment Service: Historic Monuments and Buildings (ESHMB) initiated a program of bog-clearance in August 1994 to excavate the stone circles. This work was completed by October 1994 and the excavated site was surveyed in August 1995. Almost immediately, the rate at which the stones forming the circles were breaking down was noted and a program of study initiated to make recommendations upon the conservation of this important site. Digital photogrammetric techniques were applied to aerial images of the stone circles and digital terrain models created from the images at a range of scales. These provide base data sets for comparison with identical surveys to be completed in successive years and will allow the rate of deterioration, and the areas most affected, of the circles to be determined. In addition, a 2D analysis of the stones provides an accurate analysis of the absolute 2D dimensions of the stones for rapid desktop computer analysis by researchers remote from the digital photogrammetric workstation used in the survey.

The products of this work are readily incorporated into web sites, educational packages and databases. The technique provides a rapid and user friendly method of presentation of a large body of information and measurements, and a reliable method of storage of the information from Copney should it become necessary to re-cover the site.

Knowledge Management Techniques to Augment Textual CBR (PhD Thesis)

The past decade had witnessed an unprecedented growth in the amount of available digital content, and its volume is expected to continue to grow the next few years. Unstructured text data generated from web and enterprise sources form a large fraction of such content. Many of these contain large volumes of reusable data such as solutions to frequently occurring problems, and general know-how that may be reused in appropriate contexts. In this work, we address issues around leveraging unstructured text data from sources as diverse as the web and the enterprise within the Case-based Reasoning framework. Case-based Reasoning (CBR) provides a framework and methodology for systematic reuse of historical knowledge that is available in the form of problemsolution
pairs, in solving new problems. Here, we consider possibilities of enhancing Textual CBR systems under three main themes: procurement, maintenance and retrieval. We adapt and build upon the stateof-the-art techniques from data mining and natural language processing in addressing various challenges therein. Under procurement, we investigate the problem of extracting cases (i.e., problem-solution pairs) from data sources such as incident/experience
reports. We develop case-base maintenance methods specifically tuned to text targeted towards retaining solutions such that the utility of the filtered case base in solving new problems is maximized. Further, we address the problem of query suggestions for textual case-bases and show that exploiting the problem-solution partition can enhance retrieval effectiveness by prioritizing more useful query suggestions. Additionally, we illustrate interpretable clustering as a tool to drill-down to domain specific text collections (since CBR systems are usually very domain specific) and develop techniques for improved similarity assessment in social media sources such as microblogs. Through extensive empirical evaluations, we illustrate the improvements that we are able to
achieve over the state-of-the-art methods for the respective tasks.