Matching Items (6)
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- All Subjects: Optimization
- Creators: Fox, Peter
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
In the recent past, Iraq was considered relatively rich considering its water resources compared to its surroundings. Currently, the magnitude of water resource shortages in Iraq represents an important factor in the stability of the country and in protecting sustained economic development. The need for a practical, applicable, and sustainable river basin management for the Tigris and Euphrates Rivers in Iraq is essential. Applicable water resources allocation scenarios are important to minimize the potential future water crises in connection with water quality and quantity. The allocation of the available fresh water resources in addition to reclaimed water to different users in a sustainable manner is of the urgent necessities to maintain good water quantity and quality.
In this dissertation, predictive water allocation optimization models were developed which can be used to easily identify good alternatives for water management that can then be discussed, debated, adjusted, and simulated in greater detail. This study provides guidance for decision makers in Iraq for potential future conditions, where water supplies are reduced, and demonstrates how it is feasible to adopt an efficient water allocation strategy with flexibility in providing equitable water resource allocation considering alternative resource. Using reclaimed water will help in reducing the potential negative environmental impacts of treated or/and partially treated wastewater discharges while increasing the potential uses of reclaimed water for agriculture and other applications. Using reclaimed water for irrigation is logical and efficient to enhance the economy of farmers and the environment while providing a diversity of crops, especially since most of Iraq’s built or under construction wastewater treatment plants are located in or adjacent to agricultural lands. Adopting an optimization modelling approach can assist decision makers, ensuring their decisions will benefit the economy by incorporating global experiences to control water allocations in Iraq especially considering diminished water supplies.
In this dissertation, predictive water allocation optimization models were developed which can be used to easily identify good alternatives for water management that can then be discussed, debated, adjusted, and simulated in greater detail. This study provides guidance for decision makers in Iraq for potential future conditions, where water supplies are reduced, and demonstrates how it is feasible to adopt an efficient water allocation strategy with flexibility in providing equitable water resource allocation considering alternative resource. Using reclaimed water will help in reducing the potential negative environmental impacts of treated or/and partially treated wastewater discharges while increasing the potential uses of reclaimed water for agriculture and other applications. Using reclaimed water for irrigation is logical and efficient to enhance the economy of farmers and the environment while providing a diversity of crops, especially since most of Iraq’s built or under construction wastewater treatment plants are located in or adjacent to agricultural lands. Adopting an optimization modelling approach can assist decision makers, ensuring their decisions will benefit the economy by incorporating global experiences to control water allocations in Iraq especially considering diminished water supplies.
ContributorsAhmed, Ahmed Abdulrazzaq (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Thesis advisor) / Mascaro, Giuseppe (Committee member) / Muenich, Rebecca (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
Description
Bioretention basins are a common stormwater best management practice (BMP) used to mitigate the hydrologic consequences of urbanization. Dry wells, also known as vadose-zone wells, have been used extensively in bioretention basins in Maricopa County, Arizona to decrease total drain time and recharge groundwater. A mixed integer nonlinear programming (MINLP) model has been developed for the minimum cost design of bioretention basins with dry wells.
The model developed simultaneously determines the peak stormwater inflow from watershed parameters and optimizes the size of the basin and the number and depth of dry wells based on infiltration, evapotranspiration (ET), and dry well characteristics and cost inputs. The modified rational method is used for the design storm hydrograph, and the Green-Ampt method is used for infiltration. ET rates are calculated using the Penman Monteith method or the Hargreaves-Samani method. The dry well flow rate is determined using an equation developed for reverse auger-hole flow.
The first phase of development of the model is to expand a nonlinear programming (NLP) for the optimal design of infiltration basins for use with bioretention basins. Next a single dry well is added to the NLP bioretention basin optimization model. Finally the number of dry wells in the basin is modeled as an integer variable creating a MINLP problem. The NLP models and MINLP model are solved using the General Algebraic Modeling System (GAMS). Two example applications demonstrate the efficiency and practicality of the model.
The model developed simultaneously determines the peak stormwater inflow from watershed parameters and optimizes the size of the basin and the number and depth of dry wells based on infiltration, evapotranspiration (ET), and dry well characteristics and cost inputs. The modified rational method is used for the design storm hydrograph, and the Green-Ampt method is used for infiltration. ET rates are calculated using the Penman Monteith method or the Hargreaves-Samani method. The dry well flow rate is determined using an equation developed for reverse auger-hole flow.
The first phase of development of the model is to expand a nonlinear programming (NLP) for the optimal design of infiltration basins for use with bioretention basins. Next a single dry well is added to the NLP bioretention basin optimization model. Finally the number of dry wells in the basin is modeled as an integer variable creating a MINLP problem. The NLP models and MINLP model are solved using the General Algebraic Modeling System (GAMS). Two example applications demonstrate the efficiency and practicality of the model.
ContributorsLacy, Mason (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Wang, Zhihua (Committee member) / Arizona State University (Publisher)
Created2016
Description
Vegetative filter strips (VFS) are an effective methodology used for storm water management particularly for large urban parking lots. An optimization model for the design of vegetative filter strips that minimizes the amount of land required for stormwater management using the VFS is developed in this study. The resulting optimization model is based upon the kinematic wave equation for overland sheet flow along with equations defining the cumulative infiltration and infiltration rate.
In addition to the stormwater management function, Vegetative filter strips (VFS) are effective mechanisms for control of sediment flow and soil erosion from agricultural and urban lands. Erosion is a major problem associated with areas subjected to high runoffs or steep slopes across the globe. In order to effect economy in the design of grass filter strips as a mechanism for sediment control & stormwater management, an optimization model is required that minimizes the land requirements for the VFS. The optimization model presented in this study includes an intricate system of equations including the equations defining the sheet flow on the paved and grassed area combined with the equations defining the sediment transport over the vegetative filter strip using a non-linear programming optimization model. In this study, the optimization model has been applied using a sensitivity analysis of parameters such as different soil types, rainfall characteristics etc., performed to validate the model
In addition to the stormwater management function, Vegetative filter strips (VFS) are effective mechanisms for control of sediment flow and soil erosion from agricultural and urban lands. Erosion is a major problem associated with areas subjected to high runoffs or steep slopes across the globe. In order to effect economy in the design of grass filter strips as a mechanism for sediment control & stormwater management, an optimization model is required that minimizes the land requirements for the VFS. The optimization model presented in this study includes an intricate system of equations including the equations defining the sheet flow on the paved and grassed area combined with the equations defining the sediment transport over the vegetative filter strip using a non-linear programming optimization model. In this study, the optimization model has been applied using a sensitivity analysis of parameters such as different soil types, rainfall characteristics etc., performed to validate the model
ContributorsKhatavkar, Puneet N (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Wang, Zhihua (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2015
Description
A model is presented for real-time, river-reservoir operation systems. It epitomizes forward-thinking and efficient approaches to reservoir operations during flooding events. The optimization/simulation includes five major components. The components are a mix of hydrologic and hydraulic modeling, short-term rainfall forecasting, and optimization and reservoir operation models. The optimization/simulation model is designed for ultimate accessibility and efficiency. The optimization model uses the meta-heuristic approach, which has the capability to simultaneously search for multiple optimal solutions. The dynamics of the river are simulated by applying an unsteady flow-routing method. The rainfall-runoff simulation uses the National Weather Service NexRad gridded rainfall data, since it provides critical information regarding real storm events. The short-term rainfall-forecasting model utilizes a stochastic method. The reservoir-operation is simulated by a mass-balance approach. The optimization/simulation model offers more possible optimal solutions by using the Genetic Algorithm approach as opposed to traditional gradient methods that can only compute one optimal solution at a time. The optimization/simulation was developed for the 2010 flood event that occurred in the Cumberland River basin in Nashville, Tennessee. It revealed that the reservoir upstream of Nashville was more contained and that an optimal gate release schedule could have significantly decreased the floodwater levels in downtown Nashville. The model is for demonstrative purposes only but is perfectly suitable for real-world application.
ContributorsChe, Daniel C (Author) / Mays, Larry W. (Thesis advisor) / Fox, Peter (Committee member) / Wang, Zhihua (Committee member) / Lansey, Kevin (Committee member) / Wahlin, Brian (Committee member) / Arizona State University (Publisher)
Created2015