Matching Items (5)
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- All Subjects: urban planning
- All Subjects: Carbon Sequestration
- Genre: Academic theses
- Creators: Chester, Mikhail
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 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
Description
Infrastructure are increasingly being recognized as too rigid to quickly adapt to a changing climate and a non-stationary future. This rigidness poses risks to and impacts on infrastructure service delivery and public welfare. Adaptivity in infrastructure is critical for managing uncertainties to continue providing services, yet little is known about how infrastructure can be made more agile and flexible towards improved adaptive capacity. A literature review identified approximately fifty examples of novel infrastructure and technologies which support adaptivity through one or more of ten theoretical competencies of adaptive infrastructure. From these examples emerged several infrastructure forms and possible strategies for adaptivity, including smart technologies, combined centralized/decentralized organizational structures, and renewable electricity generation. With institutional and cultural support, such novel structures and systems have the potential to transform infrastructure provision and management.
ContributorsGilrein, Erica (Author) / Chester, Mikhail (Thesis advisor) / Garcia, Margaret (Committee member) / Allenby, Braden (Committee member) / Arizona State University (Publisher)
Created2018
Description
As urban populations rapidly increase in an era of climate change and multiple social and environmental uncertainties, scientists and governments are cultivating knowledge and solutions for the sustainable growth and maintenance of cities. Although substantial literature focuses on urban water resource management related to both human and ecological sustainability, few studies assess the unique role of waterway restorations to bridge anthropocentric and ecological concerns in urban environments. To address this gap, my study addressed if well-established sustainability principles are evoked during the nascent discourse of recently proposed urban waterway developments along over fifty miles of Arizona’s Salt River. In this study, a deductive content analysis is used to illuminate the emergence of sustainability principles, the framing of the redevelopment, and to illuminate macro-environmental discourses. Three sustainability principles dominated the discourse: civility and democratic governance; livelihood sufficiency and opportunity; and social-ecological system integrity. These three principles connected to three macro-discourses: economic rationalism; democratic pragmatism; and ecological modernity. These results hold implications for policy and theory and inform urban development processes for improvements to sustainability. As continued densification, in-fill and rapid urbanization continues in the 21st century, more cities are looking to reconstruct urban riverways. Therefore, the emergent sustainability discourse regarding potential revitalizations along Arizona’s Salt River is a manifestation of how waterways are perceived, valued, and essential to urban environments for anthropocentric and ecological needs.
ContributorsHorvath, Veronica (Author) / White, Dave D (Thesis advisor) / Mirumachi, Naho (Committee member) / Childers, Dan (Committee member) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2019
Description
Bicyclist and pedestrian safety is a growing concern in San Francisco, CA,
especially given the increasing numbers of residents choosing to bike and walk. Sharing
the roads with automobiles, these alternative road users are particularly vulnerable to
sustain serious injuries. With this in mind, it is important to identify the factors that
influence the severity of bicyclist and pedestrian injuries in automobile collisions. This
study uses traffic collision data gathered from California Highway Patrol’s Statewide
Integrated Traffic Records System (SWITRS) to predict the most important
determinants of injury severity, given that a collision has occurred. Multivariate binomial
logistic regression models were created for both pedestrian and bicyclist collisions, with
bicyclist/pedestrian/driver characteristics and built environment characteristics used as
the independent variables. Results suggest that bicycle infrastructure is not an important
predictor of bicyclist injury severity, but instead bicyclist age, race, sobriety, and speed
played significant roles. Pedestrian injuries were influenced by pedestrian and driver age
and sobriety, crosswalk use, speed limit, and the type of vehicle at fault in the collision.
Understanding these key determinants that lead to severe and fatal injuries can help
local communities implement appropriate safety measures for their most susceptible
road users.
especially given the increasing numbers of residents choosing to bike and walk. Sharing
the roads with automobiles, these alternative road users are particularly vulnerable to
sustain serious injuries. With this in mind, it is important to identify the factors that
influence the severity of bicyclist and pedestrian injuries in automobile collisions. This
study uses traffic collision data gathered from California Highway Patrol’s Statewide
Integrated Traffic Records System (SWITRS) to predict the most important
determinants of injury severity, given that a collision has occurred. Multivariate binomial
logistic regression models were created for both pedestrian and bicyclist collisions, with
bicyclist/pedestrian/driver characteristics and built environment characteristics used as
the independent variables. Results suggest that bicycle infrastructure is not an important
predictor of bicyclist injury severity, but instead bicyclist age, race, sobriety, and speed
played significant roles. Pedestrian injuries were influenced by pedestrian and driver age
and sobriety, crosswalk use, speed limit, and the type of vehicle at fault in the collision.
Understanding these key determinants that lead to severe and fatal injuries can help
local communities implement appropriate safety measures for their most susceptible
road users.
ContributorsMcIntyre, Andrew (Author) / Salon, Deborah (Thesis advisor) / Kuby, Mike (Committee member) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2016