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- All Subjects: Hydraulic engineering
- Creators: Fox, Peter
- Resource Type: Text
- 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
Flooding is a critical issue around the world, and the absence of comprehension of watershed hydrologic reaction results in lack of lead-time for flood forecasting and expensive harm to property and life. It happens when water flows due to extreme rainfall storm, dam breach or snowmelt exceeds the capacity of river system reservoirs and channels. The objective of this research was to develop a methodology for determining a time series operation for releases through control gates of river-reservoir systems during flooding events in a real-time using one- and/or two-dimensional modeling of flows through river-reservoir systems.
The optimization-simulation methodology interfaces several simulation-software coupled together with an optimization model solved by genetic algorithm coded in MATLAB. These software include the U.S. Army Corps of Engineers HEC-RAS linked the genetic algorithm in MATLAB to come up with an optimization-simulation model for time series gate openings to control downstream elevations. The model involves using the one- and two-dimensional ability in HEC-RAS to perform hydrodynamic routing with high-resolution raster Digital Elevation Models. Also, the model uses both real-time gridded- and gaged-rainfall data in addition to a model for forecasting future rainfall-data.
This new model has been developed to manage reservoir release schedules before, during, and after an extraordinary rainfall event that could cause extreme flooding. Further to observe and control downstream water surface elevations to avoid exceedance of threshold of flood levels in target cells in the downstream area of study, and to minimize the damage and direct effects in both the up and downstream.
The application of the complete optimization-simulation model was applied to a portion of the Cumberland River System in Nashville, Tennessee for the flooding event of May 2010. The objective of this application is to demonstrate the applicability of the model for minimizing flood damages for an actual flood event in real-time on an actual river basin. The purpose of the application in a real-time framework would be to minimize the flood damages at Nashville, Tennessee by keeping the flood stages under the 100-year flood stage. This application also compared the three unsteady flow simulation scenarios: one-dimensional, two-dimensional and combined one- and two-dimensional unsteady flow.
The optimization-simulation methodology interfaces several simulation-software coupled together with an optimization model solved by genetic algorithm coded in MATLAB. These software include the U.S. Army Corps of Engineers HEC-RAS linked the genetic algorithm in MATLAB to come up with an optimization-simulation model for time series gate openings to control downstream elevations. The model involves using the one- and two-dimensional ability in HEC-RAS to perform hydrodynamic routing with high-resolution raster Digital Elevation Models. Also, the model uses both real-time gridded- and gaged-rainfall data in addition to a model for forecasting future rainfall-data.
This new model has been developed to manage reservoir release schedules before, during, and after an extraordinary rainfall event that could cause extreme flooding. Further to observe and control downstream water surface elevations to avoid exceedance of threshold of flood levels in target cells in the downstream area of study, and to minimize the damage and direct effects in both the up and downstream.
The application of the complete optimization-simulation model was applied to a portion of the Cumberland River System in Nashville, Tennessee for the flooding event of May 2010. The objective of this application is to demonstrate the applicability of the model for minimizing flood damages for an actual flood event in real-time on an actual river basin. The purpose of the application in a real-time framework would be to minimize the flood damages at Nashville, Tennessee by keeping the flood stages under the 100-year flood stage. This application also compared the three unsteady flow simulation scenarios: one-dimensional, two-dimensional and combined one- and two-dimensional unsteady flow.
ContributorsAlbo-Salih, Hasan Hadi Kraidi (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2019
Description
One of the two objectives of this dissertation is an investigation into the possible correlation between rainfall events and increased levels of E. coli and Mycobacterium using an existing data set. The literature states that levels of microbial concentrations do increase after rainfall events, but there are no studies to indicate this correlation applies in any Arizona water systems. The data analyzed for the bacterial concentrations project suggested the possibility of a correlation along one river but it is not conclusive to state that any correlation exists between rainfall events and the microbial concentration for many other sites included in the analysis. This is most likely due to the highly engineered water delivery systems that are not directly impacted.
The secondary objective was to determine if there are environmental variables collected from an ongoing project which would be a good candidate for making predictions about any of the project data parameters. Of the 79 possible opportunities for the model to accurately predict the dependent variable, it showed strong statistical favorability as well as experimentally favorable results towards Dissolved Organic Carbon as the best dependent variable from the data set, resulting in an accuracy of 41%. This is relevant since Dissolved Organic Carbon is one of the most important water quality parameters of concern for drinking water treatment plants where disinfection by-products are a limiting factor. The need for further analysis and additional data collection is an obvious result from both studies. The use of hydrograph data instead of rainfall would be a logical new direction for the heavily engineered water delivery systems.
The secondary objective was to determine if there are environmental variables collected from an ongoing project which would be a good candidate for making predictions about any of the project data parameters. Of the 79 possible opportunities for the model to accurately predict the dependent variable, it showed strong statistical favorability as well as experimentally favorable results towards Dissolved Organic Carbon as the best dependent variable from the data set, resulting in an accuracy of 41%. This is relevant since Dissolved Organic Carbon is one of the most important water quality parameters of concern for drinking water treatment plants where disinfection by-products are a limiting factor. The need for further analysis and additional data collection is an obvious result from both studies. The use of hydrograph data instead of rainfall would be a logical new direction for the heavily engineered water delivery systems.
ContributorsBuell, Andrew (Author) / Fox, Peter (Thesis advisor) / Abbaszadegan, Morteza (Thesis advisor) / Alum, Absar (Committee member) / Arizona State University (Publisher)
Created2018
Description
The phrase water-energy nexus is commonly used to describe the inherent and critical interdependencies between the electric power system and the water supply systems (WSS). The key interdependencies between the two systems are the power plant’s requirement of water for the cooling cycle and the water system’s need of electricity for pumping for water supply. While previous work has considered the dependency of WSS on the electrical power, this work incorporates into an optimization-simulation framework, consideration of the impact of short and long-term limited availability of water and/or electrical energy.
This research focuses on the water supply system (WSS) facet of the multi-faceted optimization and control mechanism developed for an integrated water – energy nexus system under U.S. National Science Foundation (NSF) project 029013-0010 CRISP Type 2 – Resilient cyber-enabled electric energy and water infrastructures modeling and control under extreme mega drought scenarios. A water supply system (WSS) conveys water from sources (such as lakes, rivers, dams etc.) to the treatment plants and then to users via the water distribution systems (WDS) and/or water supply canal systems (WSCS). Optimization-simulation methodologies are developed for the real-time operation of water supply systems (WSS) under critical conditions of limited electrical energy and/or water availability due to emergencies such as extreme drought conditions, electric grid failure, and other severe conditions including natural and manmade disasters. The coupling between WSS and the power system was done through alternatively exchanging data between the power system and WSS simulations via a program control overlay developed in python.
A new methodology for WDS infrastructural-operational resilience (IOR) computation was developed as a part of this research to assess the real-time performance of the WDS under emergency conditions. The methodology combines operational resilience and component level infrastructural robustness to provide a comprehensive performance assessment tool.
The optimization-simulation and resilience computation methodologies developed were tested for both hypothetical and real example WDS and WSCS, with results depicting improved resilience for operations of the WSS under normal and emergency conditions.
This research focuses on the water supply system (WSS) facet of the multi-faceted optimization and control mechanism developed for an integrated water – energy nexus system under U.S. National Science Foundation (NSF) project 029013-0010 CRISP Type 2 – Resilient cyber-enabled electric energy and water infrastructures modeling and control under extreme mega drought scenarios. A water supply system (WSS) conveys water from sources (such as lakes, rivers, dams etc.) to the treatment plants and then to users via the water distribution systems (WDS) and/or water supply canal systems (WSCS). Optimization-simulation methodologies are developed for the real-time operation of water supply systems (WSS) under critical conditions of limited electrical energy and/or water availability due to emergencies such as extreme drought conditions, electric grid failure, and other severe conditions including natural and manmade disasters. The coupling between WSS and the power system was done through alternatively exchanging data between the power system and WSS simulations via a program control overlay developed in python.
A new methodology for WDS infrastructural-operational resilience (IOR) computation was developed as a part of this research to assess the real-time performance of the WDS under emergency conditions. The methodology combines operational resilience and component level infrastructural robustness to provide a comprehensive performance assessment tool.
The optimization-simulation and resilience computation methodologies developed were tested for both hypothetical and real example WDS and WSCS, with results depicting improved resilience for operations of the WSS under normal and emergency conditions.
ContributorsKhatavkar, Puneet (Author) / Mays, Larry W. (Thesis advisor) / Vittal, Vijay (Committee member) / Mascaro, Giuseppe (Committee member) / Fox, Peter (Committee member) / Zhang, Junshan (Committee member) / Arizona State University (Publisher)
Created2019
Description
Carbon dioxide (CO2) is one of the most dangerous greenhouse gas. Its concentration in the atmosphere has increased to very high levels since the industrial revolution. This continues to be a threat due to increasing energy demands. 60% of the worlds global emissions come from automobiles and other such moving sources. Hence, to stay within safe limits, it is extremely important to curb current emissions and remove those which have already been emitted. Out of many available technologies, one such technology is the moisture swing based air capture technology that makes use of resin material that absorbs CO2 when it is dry and releases it when it is wet. A mathematical model was developed to better understand the mechanism of this process. In order to validate this model, numerical simulation and experimentation was done. Once the mechanism was proved, it was seen that there are many factors and parameters that govern this process. Some of these do not have definite value. To find the best fit value for these parameters, an optimized fitting routine needs to be developed that can minimize the standard deviation of the error. This thesis looks into ways in which the optimization of parameters can be done and the possible future work by using substantial data.
ContributorsChopra, Vinuta (Author) / Lackner, Klaus S (Thesis advisor) / Fox, Peter (Committee member) / Wright, Allen (Committee member) / Arizona State University (Publisher)
Created2016