Matching Items (5)
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- All Subjects: Hydrologic sciences
- All Subjects: Carbon Sequestration
- Creators: Chester, Mikhail
- 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
Cities are, at once, a habitat for humans, a center of economic production, a direct consumer of natural resources in the local environment, and an indirect consumer of natural resources at regional, national, and global scales. These processes do not take place in isolation: rather they are nested within complex coupled natural-human (CNH) systems that have nearby and distant teleconnections. Infrastructure systems—roads, electrical grids, pipelines, damns, and aqueducts, to name a few—have been built to convey and store these resources from their point of origin to their point of consumption. Traditional hard infrastructure systems are complemented by soft infrastructure, such as governance, legal, economic, and social systems, which rely upon the conveyance of information and currency rather than a physical commodity, creating teleconnections that link multiple CNH systems. The underlying structure of these systems allows for the creation of novel network methodologies to study the interdependencies, feedbacks, and timescales between direct and indirect resource consumers and producers; to identify potential vulnerabilities within the system; and to model the configuration of ideal system states. Direct and indirect water consumption provides an ideal indicator for such study because water risk is highly location-based in terms of geography, climate, economics, and cultural norms and is manifest at multiple geographic scales. Taken together, the CNH formed by economic trade and indirect water exchange networks create hydro-economic networks. Given the importance of hydro-economic networks for human well-being and economic production, this dissertation answers the overarching research question: What information do we gain from analyzing virtual water trade at the systems level rather than the component city level? Three studies are presented with case studies pertaining to the State of Arizona. The first derives a robust methodology to disaggregate indirect water flows to subcounty geographies. The second creates city-level metrics of hydro-economic vulnerability and functional diversity. The third analyzes the physical, legal, and economic allocation of a shared river basin to identify vulnerable nodes in river basin hydro-economic networks. This dissertation contributes to the literature through the creation of novel metrics to measure hydro-economic network properties and to generate insight into potential US hydro-economic shocks.
ContributorsRushforth, Richard Ray (Author) / Ruddell, Benajmin L (Thesis advisor) / Allenby, Braden (Committee member) / Chester, Mikhail (Committee member) / Seager, Thomas (Committee member) / Arizona State University (Publisher)
Created2016
Description
Weather radars provide quantitative precipitation estimates (QPEs) with seamless spatial coverage that can complement limitations of sparse rain gage measurements, including those affecting intensity-duration-frequency (IDF) relations used for infrastructure design. The goal of this M.S. thesis is to assess the ability of 4-km, 1-h QPEs from the Stage IV analysis of the Next-Generation Radar (NEXRAD) network to reproduce the statistics of extreme precipitation (P) in central Arizona, USA, using a dense network of 257 rain gages as reference. The generalized extreme value (GEV) distribution is used to model the frequency of annual P maximum series observed at gages and radar pixels for durations, d, from 1 to 24 h. Estimates of P quantiles from radar QPEs are negatively biased (-20% – -30%) for d = 1 h. The bias tends to 0 and errors are small for d ≥ 6 h, independently of the return period. The presence of scaling for the GEV location and scale parameters, needed to apply IDF scaling models, was found for both radar and gage products. Regional frequency analysis methods combined with bias correction of the GEV shape parameter allow reducing the statistical uncertainty and providing seamless spatial distribution of P quantiles at daily and subdaily durations that address limitations of current IDF relations in southwestern U.S. based on NOAA Atlas 14.
ContributorsSrivastava, Nehal Ansh (Author) / Mascaro, Giuseppe (Thesis advisor) / Chester, Mikhail (Committee member) / Garcia, Margaret (Committee member) / Papalexiou, Simon Michael (Committee member) / Arizona State University (Publisher)
Created2022
Description
The Water-Energy Nexus (WEN) is a concept that recognizes the interdependence of water and energy systems. The Phoenix metropolitan region (PMA) in Arizona has significant and potentially vulnerable WEN interactions. Future projections indicate that the population will increase and, with it, energy needs, while changes in future water demand are more uncertain. Climate change will also likely cause a reduction in surface water supply sources. Under these constraints, the expansion of renewable energy technology has the potential to benefit both water and energy systems and increase environmental sustainability by meeting future energy demands while lowering water use and CO2 emissions. However, the WEN synergies generated by renewables have not yet been thoroughly quantified, nor have the related costs been studied and compared to alternative options.Quantifying WEN intercations using numerical models is key to assessing renewable energy synergy. Despite recent advances, WEN models are still in their infancy, and research is needed to improve their accuracy and identify their limitations. Here, I highlight three research needs. First, most modeling efforts have been conducted for large-scale domains (e.g., states), while smaller scales, like metropolitan regions, have received less attention. Second, impacts of adopting different temporal (e.g., monthly, annual) and spatial (network granularity) resolutions on simulation accuracy have not been quantified. Third, the importance of simulating feedbacks between water and energy components has not been analyzed.
This dissertation fills these major research gaps by focusing on long-term water allocations and energy dispatch in the metropolitan region of Phoenix. An energy model is developed using the Low Emissions Analysis Platform (LEAP) platform and is subsequently coupled with a water management model based on the Water Evaluation and Planning (WEAP) platform. Analyses are conducted to quantify (1) the value of adopting coupled models instead of single models that are externally coupled, and (2) the accuracy of simulations based on different temporal resolutions of supply and demand and spatial granularity of the water and energy networks. The WEAP-LEAP integrated model is then employed under future climate scenarios to quantify the potential of renewable energy technologies to develop synergies between the PMA's water and energy systems.
ContributorsMounir, Adil (Author) / Mascaro, Giuseppe (Thesis advisor) / White, Dave (Committee member) / Garcia, Margaret (Committee member) / Xu, Tianfang (Committee member) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2022