Matching Items (3)
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- All Subjects: Carbon Sequestration
- All Subjects: Bipyridine
- All Subjects: Carbon dioxide pipelines
- Creators: Escobedo, Adolfo
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
Carbon Capture and Storage (CCS) is a climate stabilization strategy that prevents CO2 emissions from entering the atmosphere. Despite its benefits, impactful CCS projects require large investments in infrastructure, which could deter governments from implementing this strategy. In this sense, the development of innovative tools to support large-scale cost-efficient CCS deployment decisions is critical for climate change mitigation. This thesis proposes an improved mathematical formulation for the scalable infrastructure model for CCS (SimCCS), whose main objective is to design a minimum-cost pipe network to capture, transport, and store a target amount of CO2. Model decisions include source, reservoir, and pipe selection, as well as CO2 amounts to capture, store, and transport. By studying the SimCCS optimal solution and the subjacent network topology, new valid inequalities (VI) are proposed to strengthen the existing mathematical formulation. These constraints seek to improve the quality of the linear relaxation solutions in the branch and bound algorithm used to solve SimCCS. Each VI is explained with its intuitive description, mathematical structure and examples of resulting improvements. Further, all VIs are validated by assessing the impact of their elimination from the new formulation. The validated new formulation solves the 72-nodes Alberta problem up to 7 times faster than the original model. The upgraded model reduces the computation time required to solve SimCCS in 72% of randomly generated test instances, solving SimCCS up to 200 times faster. These formulations can be tested and then applied to enhance variants of the SimCCS and general fixed-charge network flow problems. Finally, an experience from testing a Benders decomposition approach for SimCCS is discussed and future scope of probable efficient solution-methods is outlined.
ContributorsLobo, Loy Joseph (Author) / Sefair, Jorge A (Thesis advisor) / Escobedo, Adolfo (Committee member) / Kuby, Michael (Committee member) / Middleton, Richard (Committee member) / Arizona State University (Publisher)
Created2017
Description
Members of the United States Climate Alliance, all of which have committed to the goals of the Paris Agreement, are actively pursuing ways to mitigate climate change. This project is intended to support the integration of agriculture into U.S. state and territory efforts by aiding in the creation of an agricultural policy toolkit for Alliance members in partnership with the American Farmland Trust and the Coalition on Agricultural Greenhouse Gases. My contribution was phase one of the toolkit, for which I created fourteen state profiles of existing efforts related to agriculture and climate change and used these for a comparative analysis. I also developed an outline of the toolkit based on conversations and a list of partner ideas I maintained and drafted an internal protocol to assist in development and implementation. Further, I analyzed the outline using a sustainability framework to identify additional efforts that could strengthen the toolkit’s sustainability. In April 2019 I presented my phase 1 efforts and the toolkit plans alongside my partners at a C-AGG conference. Overall, through this project, I generated forward momentum for integrating and supporting agriculture in climate change efforts
ContributorsHarmon, Anna (Author)
Created2019-05-15