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- All Subjects: Carbon Sequestration
- All Subjects: Communication
- All Subjects: Bipyridine
- Genre: Academic theses
- Status: Published
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
The 21st-century professional or knowledge worker spends much of the working day engaging others through electronic communication. The modes of communication available to knowledge workers have rapidly increased due to computerized technology advances: conference and video calls, instant messaging, e-mail, social media, podcasts, audio books, webinars, and much more. Professionals who think for a living express feelings of stress about their ability to respond and fear missing critical tasks or information as they attempt to wade through all the electronic communication that floods their inboxes. Although many electronic communication tools compete for the attention of the contemporary knowledge worker, most professionals use an electronic personal information management (PIM) system, more commonly known as an e-mail application and often the ubiquitous Microsoft Outlook program. The aim of this research was to provide knowledge workers with solutions to manage the influx of electronic communication that arrives daily by studying the workers in their working environment. This dissertation represents a quest to understand the current strategies knowledge workers use to manage their e-mail, and if modification of e-mail management strategies can have an impact on productivity and stress levels for these professionals. Today’s knowledge workers rarely work entirely alone, justifying the importance of also exploring methods to improve electronic communications within teams.
ContributorsCounts, Virginia (Author) / Parrish, Kristen (Thesis advisor) / Allenby, Braden (Thesis advisor) / Landis, Amy (Committee member) / Cooke, Nancy J. (Committee member) / Arizona State University (Publisher)
Created2018
Description
This document builds a model, the Resilience Engine, of how a given sociotechnical innovation contributes to the resilience of its society, where the failure points of that process might be, and what outcomes, resilient or entropic, can be generated by the uptake of a particular innovation. Closed systems, which tend towards stagnation and collapse, are distinguished from open systems, which through ongoing encounters with external novelty, tend towards enduring resilience. Heterotopia, a space bounded from the dominant order in which novelty is generated and defended, is put forth as the locus of innovation for systemic resilience, defined as the capacity to adapt to environmental changes. The generative aspect of the Resilience Engine lies in a dialectic between a heterotopia and the dominant system across a membrane which permits interaction while maintaining the autonomy of the new space. With a model of how innovation, taken up by agents seeking power outside the dominant order, leads to resilience, and of what generates failures of the Resilience Engine as well as successes, the model is tested against cases drawn from two key virtual worlds of the mid-2000s. The cases presented largely validate the model, but generate a crucial surprise. Within those worlds, 2008-2010 saw an abrupt cultural transformation as the dialectic stage of the Resilience Engine's operation generated victories for the dominant order over promising emergent attributes of virtual heterotopia. At least one emergent practice has been assimilated, generating systemic resilience, that of the conference backchannel. A surprise, however, comes from extensive evidence that one element never problematized in thinking about innovation, the discontent agent, was largely absent from virtual worlds. Rather, what users sought was not greater agency but the comfort of submission over the burdens of self-governance. Thus, aside from minor cases, the outcome of the operation of the Resilience Engine within the virtual worlds studied was the colonization of the heterotopic space for the metropolis along with attempts by agents both external and internal to generate maximum order. Pursuant to the Resilience Engine model, this outcome is a recipe for entropic collapse and for preventing new heterotopias from arising under the current dominant means of production.
ContributorsMcKnight, John Carter (Author) / Miller, Clark (Thesis advisor) / Hayes, Elisabeth (Committee member) / Allenby, Braden (Committee member) / Daer, Alice (Committee member) / Arizona State University (Publisher)
Created2013