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- All Subjects: Transportation--Planning
- Genre: Doctoral Dissertation
- Creators: Kuby, Michael
- Resource Type: Text
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
The development of microsimulation approaches to urban systems modeling has occurred largely in three parallel streams of research, namely, land use, travel demand and traffic assignment. However, there are important dependencies and inter-relationships between the model systems which need to be accounted to accurately and comprehensively model the urban system. Location choices affect household activity-travel behavior, household activity-travel behavior affects network level of service (performance), and network level of service, in turn, affects land use and activity-travel behavior. The development of conceptual designs and operational frameworks that represent such complex inter-relationships in a consistent fashion across behavioral units, geographical entities, and temporal scales has proven to be a formidable challenge. In this research, an integrated microsimulation modeling framework called SimTRAVEL (Simulator of Transport, Routes, Activities, Vehicles, Emissions, and Land) that integrates the component model systems in a behaviorally consistent fashion, is presented. The model system is designed such that the activity-travel behavior model and the dynamic traffic assignment model are able to communicate with one another along continuous time with a view to simulate emergent activity-travel patterns in response to dynamically changing network conditions. The dissertation describes the operational framework, presents the modeling methodologies, and offers an extensive discussion on the advantages that such a framework may provide for analyzing the impacts of severe network disruptions on activity-travel choices. A prototype of the model system is developed and implemented for a portion of the Greater Phoenix metropolitan area in Arizona to demonstrate the capabilities of the model system.
ContributorsKonduri, Karthik Charan (Author) / Pendyala, Ram M. (Thesis advisor) / Ahn, Soyoung (Committee member) / Kuby, Michael (Committee member) / Kaloush, Kamil (Committee member) / Arizona State University (Publisher)
Created2012
Description
Alternative fuel vehicles (AFVs) have seen increased attention as a way to reduce reliance on petroleum for transportation, but adoption rates lag behind conventional vehicles. One crucial barrier to their proliferation is the lack of a convenient refueling infrastructure, and there is not a consensus on how to locate initial stations. Some approaches recommend placing stations near where early adopters live. An alternate group of methods places stations along busy travel routes that drivers from across the metropolitan area traverse each day. To assess which theoretical approach is most appropriate, drivers of compressed natural gas (CNG) vehicles in Southern California were surveyed at stations while they refueled. Through GIS analysis, results demonstrate that respondents refueled on the way between their origins and destinations ten times more often than they refueled near their home, when no station satisfied both criteria. Freeway interchanges, which carry high daily passing traffic volumes in metropolitan areas, can be appropriate locations for initial stations based on these results. Stations cannot actually be built directly at these interchange sites, so suitable locations on nearby street networks must be chosen. A network GIS method is developed to assess street network locations' ability to capture all traffic passing through 72 interchanges in greater Los Angeles, using deviation from a driver's shortest path as the metric to assess a candidate site's suitability. There is variation in the ability of these locations to capture passing traffic both within and across interchanges, but only 7% of sites near interchanges can conveniently capture all travel directions passing through the interchange, indicating that an ad hoc station location strategy is unlikely to succeed. Surveys were then conducted at CNG stations near freeway interchanges to assess how drivers perceive and access refueling stations in these environments. Through comparative analysis of drivers' perceptions of stations, consideration of their choice sets, and the observed frequency of the use of a freeway to both access and leave these stations, results indicate that initial AFV stations near freeway interchanges can play an important role in regional AFV infrastructure.
ContributorsKelley, Scott (Author) / Kuby, Michael (Thesis advisor) / Wentz, Elizabeth (Committee member) / Pendyala, Ram (Committee member) / Arizona State University (Publisher)
Created2015