Matching Items (3)
Filtering by
- Genre: Academic theses
- Creators: Arizona State University
- Creators: Buttry, Daniel A
- Creators: Ranjan, Rajeev
- Creators: Yarger, Jeff
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
Waste heat energy conversion remains an inviting subject for research, given the renewed emphasis on energy efficiency and carbon emissions reduction. Solid-state thermoelectric devices have been widely investigated, but their practical application remains challenging because of cost and the inability to fabricate them in geometries that are easily compatible with heat sources. An intriguing alternative to solid-state thermoelectric devices is thermogalvanic cells, which include a generally liquid electrolyte that permits the transport of ions. Thermogalvanic cells have long been known in the electrochemistry community, but have not received much attention from the thermal transport community. This is surprising given that their performance is highly dependent on controlling both thermal and mass (ionic) transport. This research will focus on a research project, which is an interdisciplinary collaboration between mechanical engineering (i.e. thermal transport) and chemistry, and is a largely experimental effort aimed at improving fundamental understanding of thermogalvanic systems. The first part will discuss how a simple utilization of natural convection within the cell doubles the maximum power output of the cell. In the second part of the research, some of the results from the previous part will be applied in a feasibility study of incorporating thermogalvanic waste heat recovery systems into automobiles. Finally, a new approach to enhance Seebeck coefficient by tuning the configurational entropy of a mixed-ligand complex formation of copper sulfate aqueous electrolytes will be presented. Ultimately, a summary of these results as well as possible future work that can be formed from these efforts is discussed.
ContributorsGunawan, Andrey (Author) / Phelan, Patrick E (Thesis advisor) / Buttry, Daniel A (Committee member) / Mujica, Vladimiro (Committee member) / Chan, Candace K. (Committee member) / Wang, Robert Y (Committee member) / Arizona State University (Publisher)
Created2015
Description
Buildings continue to take up a significant portion of the global energy consumption, meaning there are significant research opportunities in reducing the energy consumption of the building sector. One widely studied area is waste heat recovery. The purpose of this research is to test a prototype thermogalvanic cell in the form factor of a UK metric brick sized at 215 mm × 102.5 mm × 65 mm for the experimental power output using a copper/copper(II) (Cu/Cu2+) based aqueous electrode. In this study the thermogalvanic brick uses a 0.7 M CuSO4 + 0.1 M H2SO4 aqueous electrolyte with copper electrodes as two of the walls. The other walls of the thermogalvanic brick are made of 5.588 mm (0.22 in) thick acrylic sheet. Internal to the brick, a 0.2 volume fraction minimal surface Schwartz diamond (Schwartz D) structure made of ABS, Polycarbonate-ABS (PCABS), and Polycarbonate-Carbon Fiber (PCCF) was tested to see the effects on the power output of the thermogalvanic brick. By changing the size of the thermogalvanic cell into that of a brick will allow this thermogalvanic cell to become the literal building blocks of green buildings. The thermogalvanic brick was tested by applying a constant power to the strip heater attached to the hot side of the brick, resulting in various ∆T values between 8◦C and 15◦C depending on the material of Schwartz D inside. From this, it was found that a single Cu/Cu2+ thermogalvanic brick containing the PCCF or PCABS Schwartz D performed equivalently well at a 163.8% or 164.9%, respectively, higher normalized power density output than the control brick containing only electrolyte solution.
ContributorsLee, William J. (Author) / Phelan, Patrick (Thesis advisor) / El Asmar, Mounir (Committee member) / Milcarek, Ryan (Committee member) / Arizona State University (Publisher)
Created2018