Chemistry Commons^™

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objectives of this project are to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solution, and to use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species, enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed phases 1 and 2. Phase 3 has been partially completed. The tasks have been expanded …

F-Element Electrochemistry In Room Temperature Ionic Liquids, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This proposal focuses on f-element electrochemistry in room temperature ionic liquids (RTILs). The ultimate goal is to fully characterize the oxidation/reduction of elements in RTILs to establish the baseline thermodynamic and kinetic data for these systems. The data will be used to critically evaluate the ability to use electrochemical methods for controlled, potential mediated, separation off-elements by electroplating on electrodes surfaces. Factors that will influence the ability to measure the redox processes in f-elements in RTIL solutions and electroplating on electrode surfaces include the structure, solubility, and stability of the target species in these solutions. These factors will be addressed …

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March, 2006, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. For two and a half years, research has been actively performed on this project, and is currently on schedule for the proposed timelines.

Progress:

• The electrochemical characterization of Ce and Eu complexed with EDTA, NTA, and Citrate has been completed.

• Synthesis of the polymer substrate and the chelating ligand is underway. Approximately 50 grams of disulfide has been produced to produce the chelating thiol group required for the last set of studies.

• Gold substrates have been prepared to perform …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborators, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed Phases 1 and 2.

The following were specific goals for this year:

• To develop a fundamental …

The Electrochemical Separation Of Curium And Americium: Quaterly Report April - June, 2005, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium.

Results

• We have completed the electrochemical investigation in of the Ce³⁺/Ce⁴⁺ redox couple and have determined the optimum experimental conditions.

• Computer modeling of the cerium using the JChess speciation-modeling program has been completed for the Ce redox couple. Traditional complexing ligands such as EDTA, oxalate, NTA, phosphate, acetate, and sulfate have been purchased and will be used to initiate the complexation and electrochemical characterization.

• Electrochemical investigations have continued on the Eu²⁺/Eu³⁺ redox …

Improving Performance Characteristics Of Hyphenated Preconcentrator Gc Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: A "Gold Standard" For Sensor Development, Touradj Solouski

University of Maine Office of Research Administration: Grant Reports

Professor Touradj Solouki of the University of Maine at Orono is supported by the Analytical and Surface Chemistry Program to investigate cryofocusing of analytes in an Electrospray Ionization Fourier Transform Ion Cyclotron Resonance (ESI-FT-ICR) mass spectrometer. To overcome sensitivity problems of FT-ICR, Professor Solouki has added a pre-concentration (PC) gas chromatograph (GC) step to his setup. The goal of this Small Grant for Exploratory Research is to add an additional device: a cryofocuser after the GC. This is predicted to improve the detection limit by two orders of magnitude, and mass resolving power by a factor of 5-10. The PI …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with our DOE collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing our ability to selectively target and sequester individual species from mixtures.

The following were specific goals for this year:

• To develop a fundamental understanding of the thermodynamic properties of actinide and lanthanide species such as Cm, Am, Ce, Nd, …

The Electrochemical Separation Of Curium And Americium: Quaterly Report August-December 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. The following pages outline the progress on our project to date. We have been actively performing research on this project for three months and are currently on schedule in terms of the proposed timelines.

The initial focus of the project involved setting up the laboratories for the studies outlined in the grant proposal. The instrumentation needed included an electrochemical work station that will perform the bulk of the electrochemical studies. This instrument will complement the electrochemical instrumentation in Dr. Hatchett’s laboratory and …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to develop a method for the separation of Am from Cm based on electrochemical techniques. Electrochemical systems that allow the thermodynamics of actinide and lanthanide complexes to be systematically evaluated and tuned will be examined. The influence of complex formation on the ability to selectively isolate a given species electrochemically will be evaluated. Metal-ligand complex formation provides a useful derivation technique to increase solubility in solution environments that favor precipitation. In addition, the thermodynamic properties of a complex relative to the isolated species may be shifted to more suitably measurable electrochemical separation regimes. Electrochemical …

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium.

Data collection and analysis of the Ce³⁺/Ce⁴⁺ redox couple in various supporting electrolytes has continued. All electrolyte systems were investigated at Pt, Au, and Glassy Carbon working electrodes. Analysis of these data was accomplished by performing appropriate background subtractions to reveal net peaks due to Ce redox behavior. Successful identification of the Ce redox couple was achieved with all electrolyte/electrode systems, although a decline in peak resolution was observed with increasing acid concentration. Optimal conditions in this experiment were …

The Activity Of Silicon Carbide Particles In Al-Based Metal Matrix Composites Revealed By Scanning Electrochemical Microscopy, David O. Wipf, L. Díaz-Ballote, L. Veleva, M. A. Pech-Canul, M. I. Pech-Canul

College of Arts and Sciences Publications and Scholarship

Scanning electrochemical microscopy (SECM) is used to image variations in electrochemical activity over the surface of an aluminum-based metal matrix composite (MMC) in contact with buffered or unbuffered neutral solutions. The composite consists of an Al - 13.5% Si - 9% Mg alloy matrix and reinforcing silicon carbide particles (SiC_p). Feedback mode SECM imaging using ferrocenemethanol as a redox mediator in 0.1 M NaCl solution and in buffer solution (pH 6.8) revealed that the SiC particles are electrochemically active. The data suggest that the electronic conductivity at these sites is higher than that of the Al₂O …

Morphologic And Magnetic Properties Of Pd₁₀₀₋ₓfeₓ Nanoparticles Prepared By Ultrasound Assisted Electrochemistry, Maribel Guzman, Jean Luc Delplancke, Gary J. Long, Jacques P. Delwiche, Marie Jeanne Hubin-Franskin, Fernande Grandjean

Chemistry Faculty Research & Creative Works

Nanopowdered alloys of Pd_100-xFe_x, with x=4, 6, 8, and 12, have been prepared by ultrasound assisted electrochemistry. The composition of the individual particles, as determined by x-ray fluorescence, and the bulk composition, as determined by atomic absorption, are in agreement within experimental error. Transmission electron microscopy indicates that the nanopowders consist of agglomerates of small grains with a radius of approximately 5 nm, a radius which is confirmed by the broadening of the reflections in the x-ray powder diffraction patterns. X-ray fluorescence analysis of individual grains indicates a homogeneous distribution of palladium and iron throughout the …

Electrochemistry And Spectroscopy Of Sulfate And Thiosulfate Complexes Of Iron Porphyrins, Philip Walter Crawford, Michael D. Ryan

Chemistry Faculty Research and Publications

The electrochemical and spectroscopic properties of the complex formed by the addition of thiosulfate to ferric porphyrins were examined. The NMR spectrum of the thiosulfate–ferric porphyrin complex was consistent with a high-spin ferric complex, while the EPR spectrum at liquid nitrogen temperatures indicated that the complex under these conditions was low-spin. Such behavior has been previously observed for other ferric porphyrin complexes. The visible spectra were characterized by a shift in the Soret band to higher energies, with smaller changes in the longer wavelength region. The complex was reasonably stable in DMF, but slowly reduced over several hours to Fe …

Observations On Lemon Cells, Jerry Goodisman

Chemistry - All Scholarship

In many general chemistry texts (1), the electrochemistry chapter is introduced with a picture of a “lemon cell”, leads of Zn and Cu piercing a lemon (or sometimes a grapefruit). A voltmeter connected across them shows a potential of about 1 V. (It has been shown how several fruits connected in series can be used to run a calculator [2].) The texts then discuss oxidation–reduction, half-cells, and the rest of what we teach freshmen about electrochemistry, and the lemon is never mentioned again.

It would appear to be questionable scientific pedagogy to present something, even something …

Impedance Feedback Control For Scanning Electrochemical Microscopy, David O. Wipf, Mario A. Apuche-Avlles

College of Arts and Sciences Publications and Scholarship

A new constant-distance imaging method based on the relationship between tip impedance and tip-substrate separation has been developed for the scanning electrochemical microscope (SECM). The tip impedance is monitored by application of a high frequency ac voltage bias between the tip and auxiliary electrode. The high frequency ac current is easily separated from the dc level faradaic electrochemistry with a simple RC filter, which allows impedance measurements during feedback or generation/collection experiments. By employing a piezo-based feedback controller we are able to maintain the impedance at a constant value and, thus, maintain a constant tip-substrate separation. Application of the method …

Use Of Excel To Obtain Voltammetric Information On Microelectrodes, Enda Howard, John Cassidy

Articles

The use of curve fitting for the analysis and interpretation of voltammetric data obtained while working with micro electrodes is discussed as a useful exercise for introducing students to the principle of problem solving using least-squares curve-fitting techniques. The advantages associated with this approach to data processing over the approach where the limiting current (i L) alone is used are discussed and its limitations are highlighted. This technique was applied to the determination of unknown concentrations of ferrocyanide and the most satisfactory recovery of concentrations was found when both the va1ues of the formal potential (EO') and concentration ( C) …

Construction Of Gold Micro-Bead Ultramicroelectrodes, Deon T. Miles, Andrew Knedlik, David O. Wipf

College of Arts and Sciences Publications and Scholarship

A new way to construct small electrodes by the use of metal micro-beads is described. Gold beads of 1.5 to 3.0 mm diameter were used to construct inexpensive and disposable microelectrodes with overall structural diameters of £ 6 mm and electrode diameters of £ 5 mm. The voltammetric response of these electrodes is consistent with existing theory and the electrodes exhibited the sigmoidal waves expected at ultramicroelectrodes.

Ohmic Drop Compensation In Voltammetry:  Iterative Correction Of The Applied Potential, David O. Wipf

College of Arts and Sciences Publications and Scholarship

A new method of ohmic potential drop correction for use with potential step and sweep voltammetric methods is described. The method, iterative correction of the applied potential (ICAP), essentially replaces an electronic positive feedback correction with a digital positive feedback correction. This paper will present one form of the ICAP procedure, in which voltammetric current data acquired by a high-speed digital oscilloscope are used to iteratively generate a compensating potential waveform that is then synthesized by an arbitrary waveform generator. The ICAP method is advantageous for high-speed measurements, since many of the difficulties caused by electronic positive feedback compensation are …

In Situ Infrared Evidence For The Electrochemical Incorporation Of Hydrogen Into Si And Ge, K. C. Mandal, F. Ozanam, J.-N. Chazalviel

Faculty Publications

No abstract provided.

Effect Of Sodium Ions On The Electrochemical Reduction Of Diethyl Fumarate In Dimethylsulfoxide And Acetonitrile, Michael D. Ryan, Dennis H. Evans

Chemistry Faculty Research and Publications

No abstract provided.

Analysis Of Solutions For Surface Active Agents, Henry H. Bauer

KWRRI Research Reports

The objective of this study was to obtain a better understanding of the behavior of surfactants in aqueous solutions at electrodes. With this understanding it should be possible to design electrochemical methods for the detection, identification, and quantitative determination of such substances. This study was concerned primarily with the influence of extraneous salts on the behavior of surface active agents when these are examined by the electrochemical technique known as tensammetry.

The tensammetric method consists essentially of the measurement of the electrical impedance of an electrochemical cell. This impedance is characteristically increased in the presence of surfactants at those potentials …