Matching Items (4)
Filtering by

Clear all filters

153344-Thumbnail Image.png
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

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 sequestration (CCS) is one of the important mitigation options for climate change. Numerous technologies to capture carbon dioxide (CO2) are in development but currently, capture using amines is the predominant technology. When the flue gas reacts with amines (Monoethanaloamine) the CO2 is absorbed into the solution and

Carbon capture and sequestration (CCS) is one of the important mitigation options for climate change. Numerous technologies to capture carbon dioxide (CO2) are in development but currently, capture using amines is the predominant technology. When the flue gas reacts with amines (Monoethanaloamine) the CO2 is absorbed into the solution and forms an intermediate product which then releases CO2 at higher temperature. The high temperature necessary to strip CO2 is provided by steam extracted from the powerplant thus reducing the net output of the powerplant by 25% to 35%. The reduction in electricity output for the same input of coal increases the emissions factor of Nitrogen Oxides, Mercury, Particulate matter, Ammonia, Volatile organic compounds for the same unit of electricity produced. The thesis questions if this tradeoff between CO2 and other emissions is beneficial or not. Three different methodologies, Life Cycle Assessment, Valuation models and cost benefit analysis are used to identify if there is a net benefit to the society on implementation of CCS to a Pulverized coal powerplant. These methodologies include the benefits due to reduction of CO2 and the disbenefits due to the increase of other emissions. The life cycle assessment using ecoindicator'99 methodology shows the CCS is not beneficial under Hierarchical and Egalitarian perspective. The valuation model shows that the inclusion of the other emissions reduces the benefit associated with CCS. For a lower CO2 price the valuation model shows that CCS is detrimental to the environment. The cost benefit analysis shows that a CO2 price of at least $80/tCO2 is required for the cost benefit ratio to be 1. The methodology integrates Montecarlo simulation to characterize the uncertainties associated with the valuation models.
ContributorsSekar, Ashok (Author) / Williams, Eric (Thesis advisor) / Chester, Mikhail (Thesis advisor) / Allenby, Braden (Committee member) / Arizona State University (Publisher)
Created2012
156772-Thumbnail Image.png
Description

Motivated by the need for cities to prepare and be resilient to unpredictable future weather conditions, this dissertation advances a novel infrastructure development theory of “safe-to-fail” to increase the adaptive capacity of cities to climate change. Current infrastructure development is primarily reliant on identifying probable risks to engineered systems and

Motivated by the need for cities to prepare and be resilient to unpredictable future weather conditions, this dissertation advances a novel infrastructure development theory of “safe-to-fail” to increase the adaptive capacity of cities to climate change. Current infrastructure development is primarily reliant on identifying probable risks to engineered systems and making infrastructure reliable to maintain its function up to a designed system capacity. However, alterations happening in the earth system (e.g., atmosphere, oceans, land, and ice) and in human systems (e.g., greenhouse gas emission, population, land-use, technology, and natural resource use) are increasing the uncertainties in weather predictions and risk calculations and making it difficult for engineered infrastructure to maintain intended design thresholds in non-stationary future. This dissertation presents a new way to develop safe-to-fail infrastructure that departs from the current practice of risk calculation and is able to manage failure consequences when unpredicted risks overwhelm engineered systems.

This dissertation 1) defines infrastructure failure, refines existing safe-to-fail theory, and compares decision considerations for safe-to-fail vs. fail-safe infrastructure development under non-stationary climate; 2) suggests an approach to integrate the estimation of infrastructure failure impacts with extreme weather risks; 3) provides a decision tool to implement resilience strategies into safe-to-fail infrastructure development; and, 4) recognizes diverse perspectives for adopting safe-to-fail theory into practice in various decision contexts.

Overall, this dissertation advances safe-to-fail theory to help guide climate adaptation decisions that consider infrastructure failure and their consequences. The results of this dissertation demonstrate an emerging need for stakeholders, including policy makers, planners, engineers, and community members, to understand an impending “infrastructure trolley problem”, where the adaptive capacity of some regions is improved at the expense of others. Safe-to-fail further engages stakeholders to bring their knowledge into the prioritization of various failure costs based on their institutional, regional, financial, and social capacity to withstand failures. This approach connects to sustainability, where city practitioners deliberately think of and include the future cost of social, environmental and economic attributes in planning and decision-making.

ContributorsKim, Yeowon (Author) / Chester, Mikhail (Thesis advisor) / Eakin, Hallie (Committee member) / Redman, Charles (Committee member) / Miller, Thaddeus R. (Committee member) / Arizona State University (Publisher)
Created2018
157639-Thumbnail Image.png
Description
Sustainable food systems have been studied extensively in recent times and the Food-Energy-Water (FEW) nexus framework has been one of the most common frameworks used. The dissertation intends to examine and quantitatively model the food system interaction with the energy system and the water system. Traditional FEW nexus studies have

Sustainable food systems have been studied extensively in recent times and the Food-Energy-Water (FEW) nexus framework has been one of the most common frameworks used. The dissertation intends to examine and quantitatively model the food system interaction with the energy system and the water system. Traditional FEW nexus studies have focused on food production alone. While this approach is informative, it is insufficient since food is extensively traded. Various food miles studies have highlighted the extensive virtual energy and virtual water footprint of food. This highlights the need for transport, and storage needs to be considered as part of the FEW framework. The Life cycle assessment (LCA) framework is the best available option to estimate the net energy and water exchange between the food, energy, and water systems. Climate plays an important role in food production as well as food preservation. Crops are very sensitive to temperature changes and it directly impacts a crop’s productivity. Changing temperatures directly impact crop productivity, and water demand. It is important to explore the feasibility of mitigation measures to keep in check increasing agricultural water demands. Conservation technologies may be able to provide the necessary energy and water savings. Even under varying climates it might be possible to meet demand for food through trade. The complex trade network might have the capacity to compensate for the produce lost due to climate change, and hence needs to be established. Re-visualizing the FEW nexus from the consumption perspective would better inform policy on exchange of constrained resources as well as carbon footprints. This puts the FEW nexus research space a step towards recreating the FEW nexus as a network of networks, that is, FEW-e (FEW exchange) nexus.
ContributorsNatarajan, Mukunth (Author) / Chester, Mikhail (Thesis advisor) / Lobo, Jose (Committee member) / Ruddell, Benjamin (Committee member) / Fraser, Andrew (Committee member) / Arizona State University (Publisher)
Created2019